Boron Co-doping Research Articles

Potassium and Boron Co-Doping of g-C3N4 Tuned CO2 Reduction Mechanism for Enhanced Photocatalytic Performance: A First-Principles Investigation

Graphitic phase carbon nitride (g-C3N4, abbreviated as CN) can be used as a photocatalyst to reduce the concentration of atmospheric carbon dioxide. However, there is still potential for improvement in the small band gap and carrier migration properties of intrinsic materials. K-B co-doped CN (KBCN) was investigated as a promising photocatalyst for carbon dioxide reduction via the Density Functional Theory (DFT) method. The electronic and optical properties of CN and KBCN indicate that doping K and B can improve the catalytic performance of CN by promoting charge migration and separation. In terms of the Gibbs free energy change, the CO2 reduction reaction catalysed by KBCN results in CH3OH, and its optimal pathway is CO2 → *CO2 → *COOH → CO → *OCH → HCHO → *OCH3 → CH3OH. Compared with CN, the doping elements K and B shift the rate-determining step from CO2 → *CO2 to *CO2 → *COOH. The K and B elements co-doping tuned the charge distribution between the catalyst and the adsorbate and reduced the Gibbs free energy of the rate-determining step from 1.571 to 0.861 eV, suggesting that the CO2 reduction activity of KBCN is superior to that of CN. Our work provides useful insights for the design of metallic–nonmetallic co-doped CN for photocatalytic CO2 reduction (CO2PR) reactions.

Boron/phosphorus co-doped nitrogen-rich carbon nanofiber with flexible anode for robust sodium-ion battery

Flexible energy storage devices have been paid much attention and adapts to apply in various fields. Benefiting from the active sites of boron (B) and phosphorus (P) doping materials, co-doped carbon materials are widely used in energy storage devices for the enhanced electrochemical performance. Herein, B and P co-doped flexible carbon nanofibers with nitrogen-rich (B-P/NC) are investigated with electrospinning for sodium-ion battery. The flexible of binderless B-P/NC with annealing of 600 °C (B-P/NC-600) exhibits the remarkable performance for the robust capacity of 200 mAh/g at 0.1 A/g after 500 cycles and a durable reversible capacity of 160 mAh/g even at 1 A/g after 12,000 cycles, exhibiting the equally commendable stability of flexible B-P/NC-600. In addition, B-P/NC-600 delivers the reversible capacity of 265 mAh/g with the test temperature of 60 °C. More importantly, the flexible B-P/NC-600 is fabricated as anode for the whole battery, delivering the capacity of 90 mAh/g at 1 A/g after 200 cycles. Meanwhile, theoretical calculation further verified that boron and phosphorus co-doping can improve the adsorption capacity of nitrogen carbon materials. The favorable performance of flexible B-P/NC-600 can be ascribed to the nitrogen-rich carbon nanofibers with three-dimensional network matrix for the more active site of boron and phosphorus co-doping. Our work paves the way for the improvement of flexible anodes and wide-operating temperature of sodium-ion batteries by doping approach of much heteroatom.

Revealing the synergistic effect of bulk and surface co-doped boron on TiO2 for enhanced photocatalytic H2 evolution

Boron(B) doping is considered as a promising modification method for TiO2 photocatalyst due to the facilitation of separation and migration of photogenerated carriers. However, the modification mechanisms of bulk or surface doping modes on photocatalyst are controversial, and the catalytic activity still needs to be improved. Here, a bulk and surface B co-doped TiO2 (B(B&S)-TiO2) derived from B-containing Ti-MOF (MIL-125(B)) precursor was demonstrated, which achieved a H2 evolution rate of 9.56 mmol∙g−1∙h−1 under 365 nm light without co-catalyst. Detailed investigations reveal the synergistic effect between bulk and surface co-doped B, which optimizes the microstructure, activates the 3-coordinated O (O3C) atoms of B-Ti-O structural units as active sites, enhances the transfer of photoelectrons and inhibits the recombination, balances H* adsorption–desorption during the photocatalytic reactions. This work exhibits a novel strategy of bulk and surface B co-doped photocatalysts and highlights the potential for achieving high photocatalytic H2 evolution rate without co-catalyst.

Suppressing hydrogen embrittlement of a CrCoNi medium-entropy alloy by triggering co-segregation of carbon, boron, and Cr

The CrCoNi medium-entropy alloy has drawn extensive attention due to its outstanding mechanical properties, yet it suffers severe gaseous hydrogen embrittlement (HE). Here we report that co-doping of carbon and boron could greatly suppress such embrittlement, resulting in a significant reduction in ductility loss from 71 % to merely 16 %. The minor doping has no significant influence on the phase structure, grain size, and grain-boundary character. However, the co-segregation of carbon, boron, and Cr was triggered, which not only improves the grain-boundary cohesive strength but also hinders the diffusion and accumulation of hydrogen at GBs, thereby leading to improved HE resistance.

An efficient multi-path to active peroxymonosulfate by carbon and sulfur co-doped boron nitride for antibiotics degradation: An emerging electron-transfer pathway at activated-S sites

Metal-free catalysis is considered promising for the green degradation of aqueous organic pollutants. Herein, a novel non-metallic heteroatom-doped boron nitride (h-BN) catalyst with carbon and sulfur doping, named SC-BN, was successfully prepared. Under optimal conditions, the SC-BN/peroxymonosulfate (PMS) system can achieve an impressive 99.4 % levofloxacin removal within 90 min (kobs = 0.0531 min−1). In-depth physicochemical characterizations have identified B-N-C and C-S-C as co-active functional groups. The electrochemical characterization and density functional theory (DFT) calculations further verified the enhanced electron transfer pathway (ETP) at S sites, which was activated by an emerging electric field. h-BN as a highly electroactive material also plays a positive role in regulation. Besides, the electrical energy per order (EE/O = 6.65 kWh/m3) and toxicity evaluation results exhibited the practical potential for eco-friendly detoxification and degradation of various refractory contaminants. In summary, this study puts forth a novel metal-free PMS activation process with an efficient multi-path mechanism and provides a theoretical foundation for future research.

Boron and Nitrogen Co-Doped Porous Graphene Nanostructures for the Electrochemical Detection of Poisonous Heavy Metal Ions

Heavy metal poisoning has a life-threatening impact on the human body to aquatic ecosystems. This necessitates designing a convenient green methodology for the fabrication of an electrochemical sensor that can detect heavy metal ions efficiently. In this study, boron (B) and nitrogen (N) co-doped laser-induced porous graphene (LIGBN) nanostructured electrodes were fabricated using a direct laser writing technique. The fabricated electrodes were utilised for the individual and simultaneous electrochemical detection of lead (Pb2+) and cadmium (Cd2+) ions using a square wave voltammetry technique (SWV). The synergistic effect of B and N co-doping results in an improved sensing performance of the electrode with better sensitivity of 0.725 µA/µM for Pb2+ and 0.661 µA/µM for Cd2+ ions, respectively. Moreover, the sensing electrode shows a low limit of detection of 0.21 µM and 0.25 µM for Pb2+ and Cd2+ ions, with wide linear ranges from 8.0 to 80 µM for Pb2+ and Cd2+ ions and high linearity of R2 = 0.99 in case of simultaneous detection. This rapid and facile method of fabricating heteroatom-doped porous graphene opens a new avenue in electrochemical sensing studies to detect various hazardous metal ions.

Binary nonmetal boron and phosphorus co-doping into PdRh nanosheets boosts electro‑upgrading polyethylene terephthalate

The upcycling of plastic waste through electrochemistry has garnered significant interest. In this study, we present a two-step strategy for synthesizing boron (B) and phosphorus (P) co-doped quaternary PdRhBP nanosheets (PdRhBP NSs) aimed at converting polyethylene terephthalate (PET) plastic hydrolysate (ethylene glycol) into high-value-added chemicals. The electrocatalytic performance of PdRhBP NSs for ethylene glycol (EG) oxidation surpasses that of PdRh nanosheets (PdRh NSs) and commercial Pd black. Notably, the highest contents of glycolic acid (GA) and formate are observed at a voltage of 0.755 V. This can be attributed to the two-dimensional structural advantages of PdRhBP NSs and the synergistic effect of B and P, optimizing the electronic configuration of Pd. This study not only proposes a double-doping strategy for designing efficient electrochemical conversion catalysts but also presents a green and sustainable approach for upgrading and utilizing plastic waste.

Tungsten and Boron Codoping toward High Ionic Conductivity and Stable Sodium Solid Electrolyte for All-Solid-State Sodium Batteries.

Sodium solid electrolytes with high ionic conductivity and good interfacial stability with sodium metal are crucial to realize high-performance all-solid-state sodium batteries. In this work, W and B-codoped Na3Sb1-xWxS4-xBx solid electrolytes are prepared by melt-quenching with further annealing. The synthesized Na3Sb0.95W0.05S3.95B0.05 solid electrolyte possesses a high ionic conductivity of 11.06 mS cm-1 under 25 °C and shows significantly improved interface compatibility with metal sodium. Specifically, Na/Na3Sb0.95W0.05S3.95B0.05/Na symmetric cell can stable cycle for 500 h under a current density of 0.05 mA cm-2. In addition, the resultant TiS2/Na3Sb0.95W0.05S3.95B0.05/Na battery exhibits an initial charge capacity of 164.1 mAh g-1 at 0.1 C with a capacity retention of 76.4% after 100 cycles. This work provides a new strategy to realize the high ionic conductivity of sodium solid electrolytes with improved interfacial stability with sodium anode.

First-principles study of effect of impurity compensation on optical properties of Si

Presently, impurity-compensated silicon (Si) has no clear potential applications due to high resistance and few carriers. Thus, it has received little attention from researchers. In this study, we find that impurity compensation can make localized state energy levels form in Si bandgap, which can improve the light absorption of Si in the near infrared region. In this work, in order to comprehensively and deeply understand the photoelectric properties of impurity-compensated Si, the localized state energy levels composed of P<sup>+</sup>/B<sup>–</sup> ions are constructed in Si bandgap through the co-doping of phosphorus (P) and boron (B), thereby forming impurity-compensated Si. The first-principles based on a density functional theory framework is used to study the photoelectric properties of the impurity-compensated Si (n/p-Sic) such as the density of states (DOS), dielectric function and refractive index. The DOS study reveals the following results: after the n- and p-Si with the same concentration of P and B (12.5%) are fully compensated for by impurities, the Fermi energy levels of their compensated counterparts are at the valley bottom formed by the two adjacent DOS peaks, and the DOS is not zero at the valley bottom. In the study of dielectric function and refractive index, it is found that when the doping ratio is <i>C</i><sub>B</sub>/<i>C</i><sub>P0</sub> = 0.25, n-Sic has the largest dielectric function and refractive index in the low energy region. In addition, comparing intrinsic Si with its doped counterparts in the real part (Re) of their dielectric constant, the following regularity is found: in the high energy region of <i>E</i> > 4 eV, the Re values of the intrinsic Si, n/p-Si and p-Sic are negative. In the low energy region of 0.64 eV< <i>E</i> < 1.50 eV, the Re value of n-Sic is negative for the doping ratio of <i>C</i><sub>B</sub>/<i>C</i><sub>P0</sub> = 0.25. The above comparison indicates that the n-Sic with <i>C</i><sub>B</sub>/<i>C</i><sub>P0</sub> = 0.25 can achieve good metallicity in the low energy region, indicating that the electrons in valence band are easily excited by low-energy long-wavelength light. Theoretical studies show that the good photoelectric properties of n-Sic with <i>C</i><sub>B</sub>/<i>C</i><sub>P0</sub> = 0.25 may be related to Si dangling bonds and localized state energy levels in Si bandgap. The Si dangling bonds are caused by the impurity compensation of B dopant for n-Si, leading part of Si-Si bonds to change into Si-B bonds. This study provides theoretical guidance for the application of impurity-compensated Si in the field of photodetectors such as CMOS image sensors and infrared photodetectors.

High Conductivity Hydrogenated Boron and Silicon Co-Doped Diamond With 0.46 Ω·mm Ohmic Contact Resistance

High Conductivity Hydrogenated Boron and Silicon Co-Doped Diamond With 0.46 Ω·mm Ohmic Contact Resistance

Systematic Investigation on the Synergistic Impact of Gallium (Ga)-Boron (B) Co-Doping on the Features of ZnO Films

Herein, gallium-boron co-doped ZnO (GBZO) thin films (TFs) of varying percentages of Ga and B doping content were coated on glass slides via spin-coating technique. The impact of doping content on the features of GBZO TFs was comprehensively probed in this work. The characterization results demonstrate that the doping content has a profound impact on the features of GBZO TFs. The X-ray diffraction results verify the polycrystalline nature of GBZO TFs with varying diffraction peak intensities. AFM images disclose the smooth coating of GBZO TFs with low surface roughness. UV–Vis-NIR transmittance spectra reveal that the deposited TFs exhibit high transparency over 86 % in range of 400-800 nm wavelength with excellent optical properties. The electrical resistance measurements indicate that GBZO TFs having doping concentrations of 2.5 at. % of Ga and 0.5 at. % of B has the lower resistivity, and the resistivity of the samples are strongly affected by the doping content. The obtained knowledge from this study could be useful for the fabrication of TF based optoelectronic devices.

Boron and nitrogen co-doped carbon supported cobalt nanoparticle in neutral aluminum-air battery

Abstract A boron and nitrogen co-doped carbon supported cobalt nanoparticle catalyst (CoBNC-phen) is successfully prepared. The co-doping method led to the formation of a Co–N bond, inhibiting the accumulation of Co nanoparticles. This also changes the electronic state, hence promoting oxygen reduction reaction performance. CoBNC-phen exhibits a half-wave potential of 23 mV higher than the commercial Pt/C. The power-density of the aluminum-air battery is 20% higher when CoBNC-phen is applied as the air cathode. Meanwhile, the voltage remained stable after 15 h of discharge.

B and N substitutional co-doping in 7AGNRs

On-surface synthesis of graphene nanoribbons enables engineering their electronic and magnetic properties, which sensitively depend on their precise bonding structure, morphology and chemical composition. Here, we investigate nitrogen and boron co-doping in order to better understand the effects of simultaneous chemical substitution in sites along the backbone of 7AGNRs. In a comparative analysis with the pristine system, the origin of the impurity bands that nitro-borylated systems exhibit was addressed. In addition to this, we studied the appearance of an electric dipolar moment, the charge transfer mechanism behind it and its dependence on the distance between BN centres. The high defect concentration limit and the dilute limit were investigated, along with various doping schemes with four substitutional doping sites and the possible emergence of magnetism in these systems.

A Nanograss Boron and Nitrogen Co-Doped Diamond Sensor Produced via High-Temperature Annealing for the Detection of Cadmium Ions.

The high-performance determination of heavy metal ions (Cd2+) in water sources is significant for the protection of public health and safety. We have developed a novel sensor of nanograss boron and nitrogen co-doped diamond (NGBND) to detect Cd2+ using a simple method without any masks or reactive ion etching. The NGBND electrode is constructed based on the co-doped diamond growth mode and the removal of the non-diamond carbon (NDC) from the NGBND/NDC composite. Both the enlarged surface area and enhanced electrochemical performance of the NGBND film are achievable. Scanning electron microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, cyclic voltammetry, electrochemical impedance spectroscopy, and differential pulse anodic stripping voltammetry (DPASV) were used to characterize the NGBND electrodes. Furthermore, we used a finite element numerical method to research the current density near the tip of NGBND. The NGBND sensor exhibits significant advantages for detecting trace Cd2+ via DPASV. A broad linear range of 1 to 100 μg L-1 with a low detection limit of 0.28 μg L-1 was achieved. The successful application of this Cd2+ sensor indicates considerable promise for the sensitive detection of heavy metal ions.

A new strategy for enhanced electrochemically activation of persulfate on B and Co co-modified carbon felt in flow-through system for efficient organic pollutants degradation

Electrochemical activation of persulfate (EA-PS) is gradually attracting attention as an emerging method for wastewater treatment. In this study, a novelty flow-through EA-PS system was first attempted for pollutants degradation using boron and cobalt co-doping carbon felt (B, Co-CF) as the cathode. SEM images, XPS and XRD spectra of B, Co-CF were investigated. The optimal doping ration between B and Co was 1:2. Increasing current density, PS concentration and flow rate, decreasing initial pH accelerated the removal of AO7. The mechanism involved in EA-PS were the comprehensive effect of DET, •OH and SO4•-. B, Co-CF cathode for flow-through system was stable with five cycles efficient AO7 decay performance. EA-PS in flow-through system was an efficient method with low cost and efficient pollutants degradation. This work provides a feasible strategy for synergistically enhancing PS activation and promoting the degradation of organic pollutants.

One-Pot, Optimized Microwave-Assisted Synthesis of Difunctionalized and B-N Co-Doped Carbon Dots: Structural Characterization.

In this work, we employed a novel microwave-assisted synthesis method to produce nitrogen and boron co-doped carbon dots (B-N co-doped CDs). To achieve optimal synthesis, we conducted a comprehensive parameter modulation approach, combining various synthesis temperatures, times, and precursor concentrations, while keeping the power constant at 150 W and pH 5. Using maximum fluorescence emission as our response variable, the best conditions were identified as 120 °C, 3 min, and a precursor concentration of 1 mg/mL. Characterization using field emission scanning electron microscopy revealed these CDs to have a spherical morphology with an average size of 10.9 ± 3.38 nm. Further high-resolution transmission electron microscopy showed an interplanar distance of 0.23 nm, which is in line with prior findings of CDs that present a 0.21 nm distance corresponding to the (100) plane of graphite. Optical properties were ascertained through UV-vis absorption, identifying distinct π-π* and n-π* transitions. Fluorescence spectroscopy highlighted an emission peak at 375 nm when excited at 295 nm, achieving a quantum yield of 56.7%. Fourier-transform infrared spectroscopy and Raman spectroscopy analyses confirmed the boronic acid and amine groups' presence, underscoring the graphitic nature of the core and the co-doping of boron and nitrogen. These empirical observations were compared with theoretical investigations through simulated Raman spectra, proposing a potential structure for the CDs. X-ray photoelectron spectroscopy further endorsed the co-doping of nitrogen and boron, along with the detection of the specified functional groups. All these characteristics could lend this nanomaterial to different types of applications such as fluorescent probes for a broad range of analytes and for fluorescent cell imaging.

The effect of boron co-doping on thermoluminescence and optically stimulated luminescence properties of LiMgPO4:Tb,Sm

The effect of boron co-doping on optically stimulated luminescence (OSL) and thermoluminescence (TL) properties of LiMgPO4:Tb,Sm,B prepared by solid-state reaction was studied. The structure of the prepared materials was confirmed by X-ray diffraction. The TL glow curves of samples irradiated with different doses of β rays were tested. No matter how much B is doped, the peaks at 190 or 280 °C are for a first-order kinetic glow curve. The activation energy and frequency factor remained almost unchanged with the increase of boron doping concentration, which indicated the trap centers of LiMgPO4:Tb,Sm,B were independent of boron doping concentration. The E at 190 and 280 °C are around 1.16 eV and 1.55 eV. Photo-ionization cross-section showed significant changes and the sensitivity of OSL reached a maximum for a concentration of 4 mol% with increasing of boron doping concentration. B-doping enhanced the OSL-signal with a factor 2.6 when B concentration is 4 mol%. The repeatability of the powders for OSL were also studied and the relative standard deviation was less than 1.5%. The minimal detectable dose (MDD) of LiMgPO4:Tb,Sm,B with a boron doping concentration of 4 mol% was 8.2 μGy. This material has a fast decay time, good repeatability, low MDD and has further research value.

Boosting supercapacitor performance through the facile synthesis of boron and nitrogen co-doped resin-derived carbon electrode material

In this study, we present the synthesis of porous carbon materials designated as B, N co-doped porous carbon materials (PRNB), co-doped with boron and nitrogen through a two-step carbonization process of self-made phenolic resin. Among them, urea, boric acid, and potassium oxalate were used as the heteroatom dopants and activator, respectively. The co-doping of boron and nitrogen induced a unique electronic structure, resulting in improved capacitance performance compared to single-doped materials. Moreover, the addition of potassium oxalate as an activator facilitated the etching of the carbon framework during pyrolysis. Owing to the co-doping effect of boron and nitrogen and the abundant micropores, the PRNB material exhibited a remarkably high specific capacitance of 330 F g−1 at 1 A g−1. It also displayed excellent rate performance (70 %) and stability, with only a 6 % loss after 10,000 cycles compared to other materials. The symmetric electrode based on PRNB achieved an energy density of up to 29.7 Wh kg−1 in a neutral electrolyte, which provides a novel approach for resin-derived carbon to improve electrochemical performance.

Evaluating the Activity of Neuraminidase in Bacterial Vaginosis Microflora and Imaging Sialic Acid on the Cell Membrane by Boron and Nitrogen Codoped Fluorescent Carbon Dots.

Sialic acids (SAs) are commonly located on the cell surface as terminal ends of glycoproteins and glycolipids. Neuraminidase (NEU) is a class of glycoside hydrolase enzymes that can cleave SAs from receptors. Both SA and NEU play important roles in human physiological and pathological processes of cell-cell interaction, communication, and signaling. Additionally, bacterial vaginosis (BV), a form of gynecological inflammation caused by dysbiosis of the vaginal microbiome, results in the abnormal activity of NEU in vaginal fluid. Here, we developed a novel probe for rapidly and selectively sensing SA and NEU based on a one-step prepared boron and nitrogen codoped fluorescent carbon dots (BN-CDs). The selective recognition reaction between SA and the phenylboronic acid groups on the surface of BN-CDs inhibits fluorescence emission from BN-CDs, while the NEU-catalyzed hydrolysis of SA bound on BN-CDs leads to fluorescence recovery. The probe was applied in diagnosing BV and showed consistent results to Amsel criteria. Moreover, the low cytotoxicity of BN-CDs facilitates its application in fluorescence imaging of SA on the membrane of red blood cells (RBCs) and leukemia cell lines (U937, KAS-1). The excellent sensitivity, accuracy, and applicability of the developed probe support its broad potential applications in future clinical diagnosis and treatment.

Boron and fluorine Co-doped laser-induced graphene towards high-performance micro-supercapacitors

Laser-induced graphene (LIG) has attracted extensive research as an electrode material for micro-supercapacitors (MSC). However, the low capacitive performance of LIG arising from both limited specific surface area and few active sites remains challenging. Herein, in situ doping of fluorine and boron atoms into laser-induced graphene was innovatively achieved via laser direct writing approach using boron-doped fluorinated polyimide (FB-PI) as the precursor. The porous fluorine and boron co-doped laser-induced graphene (FB-LIG) exhibits more active sites and improved wettability and significantly enhanced capacitive performance due to the synergistic effect of fluorine and boron co-doping. By tuning the weight ratio of boron to fluorine, the MSC utilizing FB-LIG as the electrode and poly(vinyl alcohol) (PVA)/H2SO4 as the gel electrolyte delivers a high areal capacitance of 49.81 mF/cm2 at a current density of 0.09 mA/cm2, 23 times higher that of MSC from commercial polyimide (PI)-based LIG, and 3 times that of MSC from fluorinated PI-based LIG. In addition, MSCs from FB-LIG possess excellent mechanical stability and flexibility, rendering them promising for flexible wearable microelectronics.