Dopant Research Articles

Anion‐Mediated Rapid and Direct Synthesis of FeNiOOH for Robust Water Oxidation

AbstractFeNiOOH is regarded as the most stable active species in the oxygen evolution reaction (OER), but the high oxidation energy of NiOOH poses a challenge to directly synthesize FeNiOOH as a real OER catalyst. Herein, an anion‐mediated kinetically controlled strategy is proposed, coupled with cation‐induced geometric topology modulation, to directly synthesis FeNiOOH with ultra‐thin, densely packed nanosheet architectures. Specifically, the Cl−‐mediated in situ generation of hypochlorous acid promotes the direct formation of NiFeOOH. Concurrently, high‐valence competitive Ru3+ mitigate electrostatic repulsion, fostering a compact and densely packed assembly of Ru/FeNiOOH nanosheet branches. Furthermore, the intrinsic electron‐capturing ability of FeOOH, in synergy with the stabilizing effect of doped Ru atoms, further promote the formation and stabilization high‐valence NiOOH. Consequently, the hierarchical Ru/FeNiOOH@NiPOx nanoarray catalyst displays exceptional OER performance, with an overpotential of 172 mV at 10 mA cm−2 and outstanding stability. This study provides a novel strategy to directly construct a real catalyst.

Static disorder in perovskite-type proton-conducting oxides BaSn1-xMxO3-x/2-(y/2)H2O (M = Ga, Sc, In, Y, La): a novel approach based on statistical analysis of numerous DFT simulated structures.

Perovskite-type proton-conducting oxides inherently include defects such as substitutional aliovalent cations, oxide ion vacancies, and interstitial protons. These defects introduce static disorder into their crystal structures. To investigate such disorder in BaSn1-xMxO3-x/2-(y/2)H2O (M = Ga, Sc, In, Y, La), we employ a novel approach based on density functional theory (DFT) simulations. This approach involves the structural optimization of a large number of relatively small, randomly constructed supercells, followed by statistical analysis of their geometric, energetic, and vibrational properties. Our key findings are as follows. The structural disorder becomes more pronounced as the dopant concentration increases, and as the dopant ionic radius increases from Sc to La. The O-H covalent bond lengths, as well as the number densities, of hydrogen atoms display clearly different distributions depending on whether the hydrogen atoms are trapped by aliovalent cations or not. The hydrogen-trapping energies appear to decrease as the geometric similarity of O-H covalent bonds between trapped and untrapped hydrogen atoms increases. Hydrogen atoms simultaneously trapped by more than one dopant atom exhibit considerable stability, potentially hindering proton diffusion at high dopant concentrations. The O-H stretching wavenumber decreases as the O-H covalent bond length increases, showing a very strong and nearly linear correlation between the two. The simulated IR absorption spectra show semi-quantitative agreement with the measured spectra. These new findings demonstrate the effectiveness of the present 'statistical' approach for investigating static disorder.

Influence of non-metals doping on the structural, electronic, optical, and photocatalytic properties of rutile TiO2 based on density functional theory computations

This study investigates the influence of non-metal doping (C, F, N, and S) on the structural, electronic, and optical properties of rutile TiO2 using Hubbard-corrected density functional theory (DFT) within the Quantum ESPRESSO code. Rutile TiO2 is a promising material for environmental remediation and renewable energy applications. However, it has a large bandgap of 3.03 eV, which confines its use to UV light. By substituting oxygen atoms with a single dopant atom, we aim to shift the absorption edge toward the visible spectrum. Our findings reveal that doping with C, N, and S results in a redshift of the bandgap, while F doping does not exhibit this effect. The imaginary part of the dielectric function indicates shifted absorption edges for C, N, and S-doped TiO2, making them suitable for photocatalytic applications. Additionally, an increased refractive index after doping suggests the presence of excess charge carriers that affect light propagation. This work provides valuable insights for experimentalists exploring non-metal doping influences on rutile TiO2 for photocatalysis.

Twisted Structure Induced Solid-State Fluorescence and Room-Temperature Phosphorescence from Furan-Based Carbon Dots.

Boron doping can effectively induce solid-state fluorescence (SSF) in carbon dots (CDs); however, research on the intrinsic mechanism underlying this phenomenon is lacking. Herein, a design strategy for boron-doped furan-based CDs is proposed, CDs with aggregation-induced emission (AIE) properties are synthesized, and the mechanism by which boron atom dopants induces SSF and room-temperature phosphorescence (RTP) is elucidated. The morphology and structural characterization of the CDs indicate that boron doping leads to structural twisting of the CDs. The AIE phenomenon of CDs arises from the inhibition of the twisted structure motions and a reduction in the nonradiative relaxation rate during the aggregation process. In addition, CDs with twisted structures exhibit a smaller overlap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO), effectively reducing the singlet-triplet splitting energy (ΔEST). CDs embedded in microcrystalline cellulose (MCC) exhibit green RTP because the nonradiative transitions are suppressed, and the excited triplet species remain stable. For the first time, this study reveals the structure-activity relationship between the twisted structure and optical properties of CDs, providing a new approach for the preparation of solid-state light-emitting CDs.

Architectural Design of a Multichannel Porous Carbon Fiber for Efficient Electromagnetic Microwave Absorption.

An ingenious microstructure of electromagnetic microwave absorption materials is crucial to achieve strong absorption and a broad bandwidth. Herein, one-dimensional (1D) carbon fibers with implantation of zero-dimensional (0D) ZIF-8-derived carbon frameworks and construction of a three-dimensional (3D) microcosmic multichannel porous structure are fabricated by electro-blown spinning, solvent-thermal reaction, and high-temperature pyrolysis techniques. The 1D carbon fiber skeleton with a multichannel structure provides a direct axial conductive pathway for charge transport, which plays an important role in dielectric loss. The 0D surface carbon frameworks offer plenty of heterogeneous interfaces to trigger intensive interfacial polarization loss and act as dihedral angles for microwave scattering. The 3D microcosmic multichannel pores can not only generate multiple reflections as much as possible to dissipate electromagnetic microwave energy but also supply huge interior cavities to improve impedance matching. Thanks to the synergistic effect of a strong electrically conductive pathway for enhancing the conductive loss, a plenteous heterogeneous interface for triggering intensive interfacial polarization loss, microcosmic multichannel pores for generating multiple reflections and improving impedance matching, and N and O atom doping for inducing dipole polarization, the optimal sample with an ingenious microstructure delivers an excellent absorption performance of a minimum reflection loss of -35.5 dB at a thickness of 5.0 mm and an effective absorption bandwidth of 6.72 GHz (10.96-17.68 GHz) at a thickness of 2.0 mm. Such a well-designed multichannel porous carbon fiber may pave the way for the exploitation of high-performance microwave absorbing materials.

First-principles study on lanthanide dopants in BaTiO3

Using first-principles calculation based on density-functional theory and density-functional perturbation theory, the microscopic structure and dielectric properties of Lanthanide (Ln) doped BaTiO3 are investigated. The doped Ln atoms exhibit significant displacement from Ba sites for charge compensation, forming off-centered configurations. This displacement is more pronounced for elements with smaller ionic radii. The change in ionic dielectric constant is strongly correlated with Ln displacement and Ln ion radius. As Ln displacement (ionic radius) increases (decreases), Ln-doped BaTiO3 has a higher ionic dielectric constant. However, regardless of the Ln species, the added Ln reduces the ionic dielectric constant compared to pristine BaTiO3.

Fluorinated reduced graphene oxide nanosheets for symmetric supercapacitor device performance

This study explores the potential of using spent lithium-ion battery anodes (graphite) for fabricating symmetric energy devices through a simple regeneration process. Specifically, the use of fluorine-doped reduced graphene oxide (RGO) nanosheets derived from waste batteries as the basis for a symmetric supercapacitor (SC) device is investigated. To enhance the electrochemical energy storage capabilities, a facile hydrothermal technique is employed to synthesize fluorinated graphene. Fluorination of the graphene sheets is successfully realized, as confirmed by the presence of boron with a 2.94 at.% fluorine-doped level, according to the Energy dispersive spectroscopy (EDS) spectrum analysis. Electrochemical analysis of the F-RGO electrode performance consistent with electric double-layer capacitance. Moreover, with a three-electrode system, the F-RGO electrode achieves a maximum specific capacitance of 207F/g under a current density of 1 A/g. A two-electrode symmetric device employing F-RGO exhibits a specific capacitance of 54F/g at 1 A/g. Furthermore, electrochemical impedance measurements demonstrate low charge transfer resistance (Rct) values, specifically 8.63 Ω for F-RGO, signifying improved electrochemical performance. Thus, fluorine atomic doping in RGO nanosheets contributes to the improvements of the specific capacitance and overall superior electrochemical performance of F-RGO, and F-RGO is a highly electrochemical active material for high-performance energy storage electrodes for SCs.

Synergy of S doping and defect construction in holey ultra-thin g-C3N4 nanosheets for improved photocatalytic hydrogen production from water

Combining the advantages of multiple strategies including morphology control, atom doping, and defect construction, the photocatalytic hydrogen evolution reaction (HER) performance of graphitic carbon nitride (g-C3N4) may be boosted significantly. Herein, holey ultra-thin g-C3N4 nanosheets (CNS-x, x = H, O, N) modified with structural vacancies and sulfur (S) dopant are synthesized through a straightforward method involving the pyrolysis of thiocyanuric acid under various gas atmospheres. The textural properties, type and concentration of structural defect, and S doping level are significantly influenced by the gas atmosphere. Remarkably, CNS-H with C, N dual defects and S-dopant exhibits the HER rate of 46.59 mmol·g−1·h−1, which is 16.68 times higher than that of bulk g-C3N4. The corresponding apparent quantum yields are 17.24 % at 420 nm and 1.90 % at 520 nm. The enhanced HER performance of CNS-H can be attributed to the combined effect of improved charge separation, extended photoabsorption, and optimized properties of the platinum cocatalyst.

Portable Colorimetric Sensor Array Based on a Porous Single‐Atom Fe Nanozyme with Different Surface Sites for Identifying Artificially Ripened Fruits

AbstractSingle‐atom nanozyme materials have demonstrated exceptional specific catalytic activity due to the atomic‐level dispersion of their active centers. However, the exploration of catalytic mechanisms for single‐atom catalysts is so far limited to the 2D surfaces of nanozymes. In this study, porous single‐atom Fe nanozyme (psaFeN) is successfully prepared through a straightforward coordination‐assisted polymerization‐assembly strategy. The psaFeN composite nanospheres are uniformly sized, exhibiting excellent dispersibility with well‐organized pore channels extending from the center to the surface. Density functional theory calculations reveal that in the psaFeN nanozyme, the (010) facets serve as the primary active surface, where Fe atoms form tri‐coordinated or tetra‐coordinated structures with doped nitrogen atoms. The (100) facets act as auxiliary reactive surfaces with tetra‐coordinated Fe─N as the active center. psaFeN exhibits excellent POD‐like activity (Km = 1.77 mM; Vmax = 173.53 × 10−⁸ M s−1). Given this exceptional bioactivity, a portable colorimetric biosensor is constructed for distinguishing artificially ripened fruits from naturally ripened ones. The sensor achieves precise discrimination with a detection limit as low as 310 nmol L−1. This study is anticipated to offer valuable insights into understanding the 3D catalytic mechanisms of single‐atom nanozymes, promoting their application in the development of robust biosensors for food safety.

S-Modified Graphitic Carbon Nitride with Double Defect Sites For Efficient Photocatalytic Hydrogen Evolution.

Graphitic carbon nitride (gC3N4) is an attractive photocatalyst for solar energy conversion due to its unique electronic structure and chemical stability. However, gC3N4 generally suffers from insufficient light absorption and rapid compounding of photogenerated charges. The introduction of defects and atomic doping can optimize the electronic structure of gC3N4 and improve the light absorption and carrier separation efficiency. Herein, the high efficiency of carbon nitride photocatalysis for hydrogen evolution in visible light is achieved by an S-modified double-deficient site strategy. Defect engineering forms abundant unsaturated sites and cyano (─C≡N), which promotes strong interlayer C─N bonding interactions and accelerates charge transport in gC3N4. S doping tunes the electronic structure of the semiconductors, and the formation of C─S─C bonds optimizes the electron-transfer paths of the C─N bonding, which enhances the absorption of visible light. Meanwhile,C≡N acts as an electron trap to capture photoexcited electrons, providing the active site for the reduction of H+ to hydrogen. The photocatalytic hydrogen evolution efficiency of SDCN (1613.5µmolg-1h-1) is 31.5 times higher than that of pristine MCN (51.2µmolg-1h-1). The charge separation situation and charge transfer mechanism of the photocatalysts are investigated in detail by a combination of experimental and theoretical calculations.

Magnetic Prediction of Doped Two-Dimensional Nanomaterials Based on Swin–ResNet

Magnetism is an important property of doped two-dimensional nanostructures. By introducing dopant atoms or molecules, the electronic structure and magnetic behavior of the two-dimensional nanostructures can be altered. However, the complexity of the doping process requires different strategies for the preparation and testing of various types, layers, and scales of doped two-dimensional materials using traditional techniques. This process is resource-intensive, inefficient, and can pose safety risks when dealing with chemically unstable materials. Deep learning-based methods offer an effective solution to overcome these challenges and improve production efficiency. In this study, a deep learning-based method is proposed for predicting the magnetism of doped two-dimensional nanostructures. An image dataset was constructed for deep learning using a publicly available database of doped two-dimensional nanostructures. The ResNet model was enhanced by incorporating the Swin Transformer module, resulting in the Swin–ResNet network architecture. A comparative analysis was conducted with various deep learning models, including ResNet, Res2net, ResneXt, and Swin Transformer, to evaluate the performance of the optimized model in predicting the magnetism of doped two-dimensional nanostructures. The optimized model demonstrated significant improvements in magnetism prediction, with a best accuracy of 0.9.

Zirconium-doped ultrathin copper nanowires for C1 and C2+ products in electrochemical CO2 reduction reaction

Cu-based nanostructures have garnered significant attention in the field of electrochemical carbon dioxide reduction (eCO2R), due to their significant activity and ability to produce a variety of value-added hydrocarbons and oxygenates. Current research efforts focus on steering eCO2R towards the formation of multi-carbon (C2+) products and elucidating the complex mechanisms of C-C coupling. One promising approach involves transition metals into Cu nanostructures. This study computationally investigates the impact of trace Zr atom doping on Cu nanostructures, specifically at the interfaces of (100) and (110) surfaces of ultrathin Cu nanowires. Our findings reveal that Zr dopants are energetically favourable and facilitate charge transfer to adjacent Cu atoms, thereby reducing the activation barriers for C-C coupling and enhancing the formation of C1 and C2 hydrocarbons. Additionally, the Zr-O interaction weakens the C-O bond, promoting C-O bond cleavage. The formation of C3 products, and the selectivity between hydrocarbons and oxygenates, are influenced by the hydrogenation sequence on different carbon atoms.

Nitrogen‑sulfur doped graphene-loaded SiO2/Co9S8 composites as anode materials for improved lithium storage

Heteroatom-doped graphene lamellae can effectively modulate the physical and chemical surface activities of Co9S8 materials. The addition of a second dopant atom, such as nitrogen (N) can further improve the composite properties. Herein, novel nitrogen‑sulfur double-doped graphene-loaded SiO2/Co9S8 composites (SiO2/Co9S8@NSG) were prepared by a one-step solvothermal method using polyethylene glycol as the carbon source and cobalt chloride hexahydrate as the cobalt source to yield a Deep Eutectic Solvents (DESs) system. The precursor was then obtained by adding tetraethyl silicate as the silicon source, thiourea as the sulfur source, and urea as the nitrogen source. The uniform distribution of Co9S8 in the N/S-doped graphene matrix formed graphene-coated SiO2 particles SiO2/Co9S8@NSG with high specific surface area, superior ionic conductivity, and elevated theoretical specific capacity. The N/S co-doped graphene matrix not only improved the electrical conductivity and hindered the adhesion of the particles, but also buffered the volume of the Co9S8 change and enhanced the electrochemical performance. The testing of SiO2/Co9S8@NSG composite as an anode for lithium-ion batteries (LIBs) revealed an impressive specific capacity with reversible capacity of 850 mA h/g after 900 cycles at a current density of 0.5 A/g and multiplicative capacity of 730 mA h/g at a current density of 0.1 A/g, confirming excellent cycling stability and a Coulombic efficiency close to 100 %. Overall, the proposed doping strategy looks promising for the development of high-performance LIBs.

Atomic doping of Alumina-based dielectric with high permittivity and breakdown field strength

High specific capacitance anode aluminum foils fabricated by introducing TiO2 to improve the permittivity (εr) of Al2O3 is one of the most effective ways to reduce the size and weight of aluminum electrolytic capacitors (AECs). However, the underlying mechanism by which the introduction of TiO2 causes capacity enhancement remains unclear. Here, a proposition is claimed that TiO2 is not directly responsible for the capacity enhancement but Al-doping TiO2 (AOT) actually. An atomically doping strategy based on atomic thermal diffusion and ionic electromigration is proposed to realize the fabrication of AOT via modulating the thermal and electric fields. Results show that the doping behavior of Al3+ induces the displacement of neighboring Ti4+ ions, which enhances the dipole polarization resulting in an increase of εr (25). Meanwhile, the diffusion of O2 and migration of O2– effectively removes the oxygen vacancy, enhancing the breakdown field strength (> 6 MV·cm−1) of dielectrics. Ultimately, the specific capacitance of anode foils is increased by about 50 % compared to those without AOT. On a brighter note, this work deepens the understanding of the capacity enhancement mechanism and will contribute to further facilitating the miniaturization of AECs.

Electronic Properties of Monolayer Graphene with Doping of Nitrogen Atom: A Density Functional Theory Study

Abstract As a material that has been widely researched, graphene is certainly interesting because it has many unique features. In its development, graphene is very promising as an optoelectronic material. However, in theory, graphene has obstacles in its development because its band gap position is zero. With various modifications in opening the band gap so that it does not have a value of zero. In the current research, structural modifications were carried out on graphene layers by doping with a number of Nitrogen atoms. The modeling was carried out using graphene with a supercell size of 4 x 4 x 1. Our calculations are based on Density Functional Theory using the PBE – GGA function for potential exchange correlation. The result is the Fermi level shifting and emergence of magnetic moment through doping with Nitrogen atoms. The results obtained certainly open up opportunities for the development of graphene.

A DFT study of SF6 decomposition products (H2S, SO2, and CS2) adsorption and detection on Pd-ZnO/SnS2 ternary composites

Real-time and accurate detection of SF6 decomposition products is a crucial approach to diagnosing internal faults of gas-insulated switchgear (GIS). However, the limited sensitivity and selectivity of SnS2 gas sensors have hindered their further development and application. This study employs density functional theory to design the optimal Pd-ZnO/SnS2 monolayer structure and investigate its adsorption behavior toward H2S, SO2, and CS2. The findings indicate that Pd atom doping and ZnO nanoparticle incorporation significantly enhance the conductivity of the SnS2 monolayer, reducing the band gap to 0.54 eV and lowering the work function by 5.019 eV. Regarding gas adsorption and sensing, the Pd-ZnO/SnS2 monolayer outperforms intrinsic SnS2 and ZnO/SnS2, showing the order in which SF6 decomposition products are selected is: CS2 > SO2 > H2S. Additionally, the sensitivity and recovery time of Pd-ZnO/SnS2 as a gas sensor were evaluated, confirming its excellent sensing performance for SO2 and CS2 detection. This study provides theoretical insights to advance the application of gas sensors in online insulation equipment monitoring.

Cu‐Doped 0D Bi2WO6 Nanoparticles for Efficient Visible‐Light‐Driven Photocatalytic Tetracycline Degradation

AbstractBismuth‐based photocatalysts have been widely employed in the photocatalytic degradation of organic pollutants in wastewater. However, the lack of rational structural design and the slow generation of active free radicals have hindered its efficiency. Here, we stabilized Bi2WO6 nanoparticles by wrapping them with hydroxyl groups, introduced metal Cu doping, and underwent an annealing process to construct Cu‐BiNP nanocatalysts with exposed active sites. Under visible light irradiation, 0.03Cu‐BiNP achieved a 94.5% TC degradation efficiency, which is 15.8 times higher than the rate of bulk BiWO. The 0D structure endows Cu‐BiNP with ample opportunities for O2 adsorption and activation, and Cu atomic doping reduces the bandgap and increases the oxygen vacancy, promoting the generation of active oxygen species. This work demonstrates the rapid charge separation and activation of O2 to generate active oxygen species by 0D bismuth‐based nanocatalysts in photocatalytic oxidation reactions, providing a scalable nanocatalyst platform for TC photocatalytic degradation.

Persistent physiological benefits from doping? Ethical implications for sports integrity.

The effects of some widely abused doping substances such as anabolic androgenic steroids (AAS) on performance are well documented, particularly in the short term, and the use of these substances is banned by various sporting authorities, with athletes sanctioned from competing for up to 4 years. However, controversy exists on whether residual physiological effects of some doping practices could persist even years after discontinuation, granting unfair advantages to athletes long after sanctions have been served. Particularly, in support of the so-called muscle memory theory, growing evidence in both animals and humans suggests that AAS administration could exert long-term effects at the muscle level, notably a higher number of myonuclei. This effect could enhance retraining/muscle remodeling capacity long after AAS cessation, thus supposing an advantage for doped athletes even +4 years after doping practices have been discontinued. If confirmed, the persistence of physiological improvements resulting from past doping practices raises serious ethical concerns in the sports field and opens the door to lifelong sanctions.

Optimizing excited state adsorption and carrier dynamics of metal doped zinc oxide by p-d orbital modulation for efficient reverse saturation absorption

Doping metals can regulate the excited state adsorption and carrier transport efficiency of ZnO through p-d orbital coupling thereby improving its nonlinear performance. Herein, the thin film coatings consisting of ZnO, and M-ZnO (M=Al, Sn, Mg) were synthesized using the magnetron sputtering technique. ZnO exhibited the granular/stick structure, while the metal dopant atoms (M) were incorporated into the ZnO lattice, resulting in a homogeneous distribution. Photoluminescence spectroscopy reveals the quenched defect emission intensity, indicating a decrease in the rate of photo-induced electron-hole pair complexation. Mg exhibits an optimized effect to promote the saturation absorption of ZnO, resulting in the enhancement of the nonlinear absorption (NLA) coefficients for M-ZnO films. Al-ZnO and Sn-ZnO films exhibit reverse saturation absorption. Theoretical simulation shows that the additions of transition metal atoms favor the electron transfer through p-d orbital modulation of ZnO. The p-d hybridization causes the metal-d orbitals to cross the Fermi level and form an electron transport channel, thereby enhancing the excited state absorption, and effectively controlling the NLA process and mechanism. The excited state absorption of the M-ZnO films significantly rises. This research demonstrates that the optimization of excited state absorption through p-d orbital modulation is a highly effective strategy for the development of efficient and superior nonlinear optical absorbers.

Study on highly selective NO2 gas sensors based on (Fe, Mo)-doped monolayer WSe2

The two-dimensional (2D) material WSe2 is frequently employed in gas sensors due to its excellent electrical properties. However, the weak interaction between the pristine WSe2 and gas molecules limits its application. Therefore, in this paper, the adsorption behavior of transition metal X (X = Fe, Mo) atom-doped monolayers WSe2 on H and O atoms and molecules of NO2, HCN, and CO gases is investigated to gain insights into the physical mechanisms of adsorbent-substrate interactions. Doping significantly improves the adsorption properties between the substrate and the gas molecules, with the best adsorption showing for NO2 gas molecules and O atoms. The relationship between transition metals and the improvement of adsorption performance is explored by the center position of transition metal d orbitals in different systems, and it is found that the higher the center position of the transition metal d band, the stronger the adsorption between adsorbent and substrate. Compared to pristine WSe2, Mo atom doping in the transition metal doped system has higher adsorption sensitivity to gas molecules and exhibits highly selective adsorption and chemisorption behaviors through high adsorption energies and electron transfer to NO2 molecules. It is demonstrated that X (X = Fe, Mo) doped WSe2 can be used as a gas-sensitive material for efficient gas detection.