Heteroatom Doping Research Articles

Hectogram-Scale Synthesis of Visible Light Excitable Room Temperature Phosphorescence Carbon Dots.

Carbon dots (CDs) based room temperature phosphorescence (RTP) materials can be prepared via facile procedures and exhibit excellent photostability and biocompatibility. Furthermore, doping of hetero-atoms into CDs can afford multiple triplet levels. The RTP emission generated from the resultant CDs always displays outstanding dynamic behaviors and even can be efficiently excited by visible light. Given this, CDs-based RTP materials not only can be used for anti-counterfeiting but also exhibit great application potential in signage and illumination fields. In this contribution, a type of B, N, and P co-doped CDs are prepared in hectogram scale. Upon excitation by UV lamp and white LED, the obtained CDs emit green and yellow RTP, respectively, the lifetime of which are 851 and 481ms, respectively. It is found that the luminescence color of the CDs can be further tuned. By controlling the degree of carbonization, the RTP color of the CDs can be facilely tuned from green to orange-red. Based on an energy transfer strategy, the luminescence color can be further tuned to red. Benefited from the dynamic and visible-excited colorful RTP emission, the application of these obtained CDs in anti-counterfeiting, fingerprint collection, and luminescent traffic signage are also explored.

Synthesis of Fe3O4 embedded LIG via laser ablation of PI/Fe(acac)3 film for enhanced electrocatalytic hydrogen evolution

Hydrogen production via electrocatalytic water splitting is generally considered as an efficient and eco-friendly strategy for energy storage. The exploration of novel electrocatalytic cathode material towards hydrogen evolution reaction (HER) has never ended. Laser induced graphene (LIG), as a cheap and porous material with large surface area, not only can be used as a carrier of active substances for collaborative catalysis towards hydrogen evolution, but also can be directly used as catalytic electrode via heteroatoms doping. We synthesized Fe3O4 embedded LIG via laser ablation of polyimide (PI)/Fe(acac)3 film and tested its HER electrocatalytic performance. An overpotential of 269 mV was obtained under the current density of 10 mA cm−2 with a slight current decay in the 10 h chronoamperometric examination in 1 M KOH electrolyte. This work provides an insight into methods of optimizing electrochemical properties and improving catalytic activity of LIG based materials. The performance of our Fe3O4 embedded LIG demonstrates the potential of LIG based materials as next generation HER electrocatalyst.

In-situ ionothermal synthesis of nanoporous carbon/oxide composites: A new key to functional separators for stable lithium-sulfur batteries

Lithium-sulfur batteries (LSBs) with high energy density are promising for energy storage. However, conventional polypropylene-based separator cannot avoid polysulfides shuttling which impedes the practical application of LSBs. Herein, an in-situ ionothermal synthesis strategy that concurrently applies ionic liquid as the solvent, template and high-yield carbon source is proposed for the facile preparation of nanoporous carbon/oxide composite separator modifiers. The composites exhibit features of high polarity, self doping, oxygen vacancy, heteroatom doping, abundant defects and high electronic conductivity. Theoretical and experimental studies suggest that the composites can efficiently trap and convert polysulfides for high-performance LSBs. Indeed, in the composite-modified LSBs with next-generation roll-to-roll dry-processed high-loading sulfur cathodes, enhanced performance is achieved, revealing the effectiveness of the composites as functional materials towards separator modification. Therefore, the proposed strategy and its delivered nanoporous composites exhibit excellent versatility and practicality for high-performance LSBs.

Luminescence performance and antioxidant properties of selenium carbon dots prepared from selenium-hyperaccumulating plants.

Heteroatom doping has become an important method to enhance the performance of traditional carbon dots in modern times. Selenium (Se) is a nonmetallic trace element with excellent redox properties and is therefore essential for health. Previous studies have mainly used pure chemicals as selenium sources to prepare selenium-doped carbon dots (Se-CDs), but the precursor pure chemicals have the disadvantages of being expensive, difficult to obtain, toxic, and having low fluorescence yields of the synthesised Se-CDs. Fortunately, our team achieved successful synthesis of selenium carbon dots, exhibiting excellent luminescence and biocompatibility through a one-step hydrothermal method using selenium-enriched natural plant Cardamine, as an alternative to selenium chemicals. This approach aims to address the limitations and high costs associated with Se-CDs precursors. Electron spin resonance spectroscopy (ESR) and cellular antioxidant tests have confirmed the protective ability of Se-CDs against oxidative damage induced by excessive reactive oxygen species (ROS). A new concept and method for synthesizing selenium carbon dots on the basis of biomass, a rationale for the antioxidant effects on human health, and a wide range of development and application possibilities were offered in this work.

Functional biochar accelerates peroxymonosulfate activation for organic contaminant degradation via the specific B–C–N configuration

Functional biochar designed with heteroatom doping facilitates the activation of peroxymonosulfate (PMS), triggering both radical and non-radical systems and thus augmenting pollutant degradation efficiency. A sequence of functional biochar, derived from hyperaccumulator (Sedum alfredii) residues, was synthesized via sequential doping with boron and nitrogen. The SABC-B@N-2 exhibited outstanding catalytic effectiveness in activating PMS to degrade the model pollutant, acid orange 7 (Kobs = 0.0655 min−1), which was 6.75 times more active than the pristine biochar and achieved notable mineralization efficiency (71.98%) at reduced PMS concentration (0.1 mM). Relative contribution evaluations, using steady-state concentrations combined with electrochemical and in situ Raman analyses, reveal that co-doping with boron and nitrogen alters the reaction pathway, transitioning from PMS activation through multiple reactive oxygen species (ROSs) to a predominantly non-radical process facilitated by electron transfer. Moreover, the previously misunderstood concept that singlet oxygen (1O2) plays a central role in the degradation of AO7 has been clarified. Correlation analysis and density functional theory calculations indicate that the distinct BCN configuration, featuring the BC2O group and pyridinic-N, is fundamental to the active site. This research substantially advances the sustainability of phytoremediation by offering a viable methodology to synthesize highly catalytic functional biochar utilizing hyperaccumulator residues.

Simultaneously Improving Energy Storage and Oxygen Evolution Reaction by Causing Regional Defects in MOF-on-MOF Derived Hollow Se-Doped CoP-Fe2P Heterojunctions.

Doping heteroatoms into metal phosphides to modify their electronic structure is an effective method, but the incomplete exposure of active sites is its inherent drawback. In this experiment, both Se doping and P vacancies are simultaneously introduced into CoP-Fe2P (named CoFe-P-Se) to enhance the internal reactivity. Benefiting from the unique hollow porous structure derived from the MOF-on-MOF template, as well as the enhanced intrinsic activity achieved by P defects and Se doping, CoFe-P-Se exhibits a high specific capacitance of 8.41 F cm-2 at a current density of 2 mA cm-2 when used as a supercapacitor electrode. When assembled into a hybrid supercapacitor with activated carbon, the energy density reaches 0.488 mWh cm-2 at a power density of 1.534 mW cm-2, and the capacity retention after 5000 charge-discharge cycles is as high as 90.65%. As an oxygen evolution reaction (OER) electrode, the CoFe-P-Se electrode shows a low overpotential of only 230 mV at a current density of 10 mA cm-2 and 278 mV at 100 mA cm-2. Additionally, it exhibits excellent stability for over 50 h at a current density of 100 mA cm-2. The designed element doping and vacancy engineering in this work will provide an insight for constructing high-performance electrodes.

Renewable biomass bougainvillea petals-derived porous carbon through KOH activation and B/N co-doping: Synergistic contribution and charge storage mechanism

Heteroatom doping and chemical/physical activation can be considered as two effective pathways to enhance the electrochemical performance of biomass-based porous carbon electrodes through distinct operating mechanisms. Herein, a series of biomass bougainvillea petal-derived carbon materials are successively synthesized by different strategies, among which BP-4 carbon material with hierarchical porous architecture is successfully fabricated through a composite strategy combining KOH activation and B/N co-doping. After a series of characterization tests of these synthesized materials, it is found that the BP-4 porous carbon possesses an appropriate graphitization degree, a large specific surface area, a suitable pore structure and high B and N contents. Due to the synergistic contribution of boosting the specific surface area by the KOH pore-forming activation process and generating additional faradic pseudocapacitance by introducing B/N functional groups, the BP-4 electrode exhibits brilliant electrochemical properties in terms of specific capacitance, rate capability, electrical conductivity and cycle life compared to other three carbon electrodes. Furthermore, the CV kinetic analysis of four carbon electrodes is systematically explored, which expounds the immense variability of charge storage mechanisms. This study offers insights for the exquisite design of biomass-based porous carbon material electrode with abundant electroactive sites and broadened electrochemical potential for the practical application of renewable natural biomass materials in energy storage.

State change of Na clusters in hard carbon electrodes and increased capacity for Na-ion batteries achieved by heteroatom doping

Although heteroatom doping is an effective method to improve the capacity of hard carbon (HC) anodes in Na-ion batteries (NIBs), the complicated structure of HC leads to uncertainty when understanding the effects of heteroatom doping on sodium storage. This study shows the effects of phosphorus and sulfur doping to HC on sodium storage using solid-state NMR to improve the capacity of HC prepared by the carbonization of resorcinol formaldehyde (RF) resin at 1100 °C. Heteroatom doping increased the battery capacity of the HC, especially the plateau capacity, but the interlayer distance of the carbon layers in the HC did not expand considerably. 23Na solid-state NMR revealed that heteroatom doping facilitates the formation of quasi-metallic sodium clusters, thereby contributing to the plateau capacity increase. The metallicity of the sodium clusters in heteroatom-doped HC samples was controlled by the amount of doped-phosphorous. XPS and 31P NMR detected various phosphorus sites such as phosphine and phosphine oxide in the carbon structure.

Synthesis and electrochemical performance of low cost nitrogen-doped carbon cryogel composites as supercapacitor electrodes

Developing cost-effective methods for synthesizing Nitrogen-doped carbon cryogels is crucial for advancing supercapacitor technology due to their enhanced electrochemical properties. Nitrogen-doped porous carbon cryogels are synthesized through the freeze-drying method by substituting resorcinol with phenol and using urea/melamine as nitrogen sources. The effect of nitrogen sources on the structure and electrochemical performance is investigated. In the case of carbon cryogel composites samples, using melamine as the nitrogen source (PMF) is more favorable than using urea (PUF), while both nitrogen-doped samples significantly outperform the undoped samples (PF). The PMF sample displays a specific surface area of 1119.00 m2 g−1, and a nitrogen content of 2.19 wt%. In the three-electrode system, the specific capacitance of the PMF sample reaches up to 247.9 F g−1 at a current density of 0.5 A g−1, and its rate performance is 85.52 %. By comparison, the PF sample exhibits specific capacitance and rate performance of 85.4 F g−1 and 33.44 % under the same parameters. The assembled symmetric supercapacitor in a buckle type system also demonstrates exceptional energy density (14.41 Wh kg−1), long-term cycle stability, and a favorable capacitance retention rate (72.2 %). These excellent electrochemical performances can be attributed to the synergistic effects of the hierarchical pore structures and heteroatoms doping.

Recent Advances on Carbon-Based Metal-Free Electrocatalysts for Energy and Chemical Conversions.

Over the last decade, carbon-based metal-free electrocatalysts (C-MFECs) have become important in electrocatalysis. This field is started thanks to the initial discovery that nitrogen atom doped carbon can function as a metal-free electrode in alkaline fuel cells. A wide variety of metal-free carbon nanomaterials, including 0D carbon dots, 1D carbon nanotubes, 2D graphene, and 3D porous carbons, has demonstrated high electrocatalytic performance across a variety of applications. These include clean energy generation and storage, green chemistry, and environmental remediation. The wide applicability of C-MFECs is facilitated by effective synthetic approaches, e.g., heteroatom doping, and physical/chemical modification. These methods enable the creation of catalysts with electrocatalytic properties useful for sustainable energy transformation and storage (e.g., fuel cells, Zn-air batteries, Li-O2 batteries, dye-sensitized solar cells), green chemical production (e.g., H2O2, NH3, and urea), and environmental remediation (e.g., wastewater treatment, and CO2 conversion). Furthermore, significant advances in the theoretical study of C-MFECs via advanced computational modeling and machine learning techniques have been achieved, revealing the charge transfer mechanism for rational design and development of highly efficient catalysts. This review offers a timely overview of recent progress in the development of C-MFECs, addressing material syntheses, theoretical advances, potential applications, challenges and future directions.

Modulation strategies of electrocatalysts for 5-hydroxymethylfurfural oxidation-assisted water splitting

To address energy shortages and environmental issues, prioritizing renewable energy development and usage is crucial. Employing renewable sources for water electrolysis offers a sustainable method for hydrogen generation. Reducing the water electrolysis potential is vital for efficient clean energy conversion and storage. Substituting the anodic oxygen evolution reaction in conventional hydrogen production from water electrolysis with the more thermodynamically favorable 5-hydroxymethylfurfural (HMF) oxidation reaction can greatly decrease overpotential and yield the valuable product 2,5-furan dicarboxylic acid. The key to this process is developing effective electrocatalysts to minimize the potential of the HMF electrooxidation-hydrogen production system. Therefore, this review provides a comprehensive introduction to the modulation strategies that affect the electronic and geometric structure of electrocatalysts for HMF oxidation-assisted water splitting. The strategies encompass heteroatom doping, defect projection, interface engineering, structural design, and multi-metal synergies. The catalysts are assessed from various angles, encompassing structural characterization, reaction mechanisms, and electrochemical performance. Finally, current challenges in the catalyst design and potential development of this promising field are proposed.

In-situ construction of ionic liquid salt-derived graphene-like dual-heteroatoms doping engineering as efficient metal-free electrocatalyst for oxygen reduction reaction

Metal-free heteroatom-doped carbon catalysts can effectively eliminate the degradation and pollution problems caused by metal dissolution. However, single heteroatom doping often restricts the regulation of geometric and electronic structures for oxygen reduction reaction (ORR) electrocatalysts. Herein, a dual atomic doping engineering to optimize the electronic structure and local coordination environment of ionic liquid salt-derived graphene-like host material as an efficient metal-free electrocatalyst for ORR. The resultant PNG catalyst with a typical nanosheets morphology with a high specific surface area and unique hierarchical porous structure. Benefiting from the uniform doping of P, N heteroatoms, graphene-like structure, optimized electronic structure and coordination environment, thus-prepared PNG-2 exhibits outstanding ORR activity, which the onset potential and half-potential are negatively shifted by around 70 mV and 46 mV, respectively, as compared to the commercial Pt/C (20 wt.%) for ORR. Furthermore, the PNG-2 exhibits the higher diffusion limiting current density, superior long-term stability as well as excellent resistance to methanol oxidation than Pt/C. Experimental studies and density functional theory (DFT) calculations reveal that the enhanced chemisorption of oxygen species (*OOH, *O and *OH) onto the P and N sites of the PNG catalysts can effectively accelerate the charge transfer kinetics and promote a favorable ORR performance.

Hierarchical multi-interface Co1-xS/Co9S8@C hollow microsphere for enhancing dielectric polarization as an efficient microwave absorber

Recently, close attention has been devoted to exploring highly efficient microwave absorbing materials (MAMs). Owing to their tunable dielectric properties and controllable structure, materials doped with heteroatoms have been regarded as promising absorbers. Herein, the Co@C, CoSe2@C, and hierarchical Co1-xS/Co9S8@C hollow microspheres were prepared using hydrothermal and subsequent carbonization, selenium, and vulcanization processes, respectively. The existence of anionic sites immensely affects the permittivity and conductivity of a composite. As a result, CoSe2@C and Co1-xS/Co9S8@C hollow microspheres showed improved conductivity and dielectric losses. Particularly, due to the multiphase transformation in the vulcanization process, the Co1-xS/Co9S8@C hollow microsphere possessed numerous heterogeneous interfaces and rich lattice defects, which led to local electronic redistribution and reinforced dielectric polarization. It exhibited a minimum reflection loss (RLmin) of −61.0 dB at a thinner thickness of 2.0 mm. This study contributes to the insight into the polarization loss mechanisms of multi-component and heteroatom doping composites and stimulates the design of high-efficiency MAMs.

Robust Nitrogen-Doped Microporous Carbon via Crown Ether-Functionalized Benzoxazine-Linked Porous Organic Polymers for Enhanced CO2 Adsorption and Supercapacitor Applications.

Nitrogen-doped carbon materials, characterized by abundant microporous and nitrogen functionalities, exhibit significant potential for carbon dioxide capture and supercapacitors. In this study, a class of porous organic polymer (POP) were successfully synthesized by linking Cr-TPA-4BZ-Br4 and tetraethynylpyrene (Py-T). The model benzoxazine monomers of Cr-TPA-4BZ and Cr-TPA-4BZ-Br4 were synthesized using the traditional three-step method [involving CH═N formation, reduction by NaBH4, and Mannich condensation]. Subsequently, the Sonogashira coupling reaction connected the Cr-TPA-4BZ-Br4 and Py-T monomers, forming Cr-TPA-4BZ-Py-POP. The successful synthesis of Cr-TPA-4BZ-Br4 and Cr-TPA-4BZ-Py-POP was confirmed through various analytical techniques. After verifying the successful synthesis of Cr-TPA-4BZ-Py-POP, carbonization and KOH activation procedures were conducted. These crucial steps led to the formation of poly(Cr-TPA-4BZ-Py-POP)-800, a carbon material with a structure akin to graphite. In practical applications, poly(Cr-TPA-4BZ-Py-POP)-800 exhibited a noteworthy CO2 adsorption capacity of 4.4 mmol/g, along with specific capacitance values of 397.2 and 159.2 F g-1 at 0.5 A g-1 (measured in a three-electrode cell) and 1 A g-1 (measured in a symmetric coin cell), respectively. These exceptional dual capabilities stem from the optimal ratio of heteroatom doping. The outstanding performance of poly(Cr-TPA-4BZ-Py-POP)-800 microporous carbon holds significant promise for addressing contemporary energy and environmental challenges, making substantial contributions to both sectors.

Electrochemical sensing of hydroquinone using green synthesized nitrogen-doped carbon dots

Xenobiotic contaminants are dreadful to the environment. Hydroquinone is one of those toxins that need to be sensed using a nonenzymatic, environmentally friendly material. This was achieved by carbon quantum dots (CQDs) synthesized using hydrothermal supported by heteroatom doping using a bare glassy carbon electrode (GCE) electrochemically. The carbon dot’s largest active surface area of 0.13 cm2, better electron transfer capability, and doping enhance the functional groups and electrostatic interaction with a Limit of Detection (LOD) of 0.112 µM.

Solid-State Electrocatalysis in Heteroatom-Doped Alloy Anode Enables Ultrafast Charge Lithium-Ion Batteries.

Electrocatalysis is generally confined to dynamic liquid-solid and gas-solid interfaces and is rarely applicable in solid-state reactions. Here, we report a paradigm shift strategy to exploit electrocatalysis to accelerate solid-state reactions in the context of lithium-ion batteries (LIBs). We employ heteroatom doping, specifically boron for silicon and sulfur for phosphorus, to catalyze electrochemical Li-alloying reactions in solid-state electrode materials. The preferential cleavage of polar dopant-host chemical bonds upon lithiation triggers chemical bond breaking of the host material. This solid-state catalysis, distinct from liquid and gas phases, requires a critical doping concentration for optimal performance. Beyond a critical concentration of ∼1 atom %, boron and sulfur doping drastically reduces activation energies and accelerates redox kinetics during lithiation/delithiation processes, leading to markedly enhanced rate performance in boron-doped silicon and sulfur-doped black/red phosphorus anode. Notably, a sulfur-doped black phosphorus anode coupled with a lithium cobalt oxide cathode achieves an ultrafast-charging battery, recharging 80% energy of a battery in 302 Wh kg-1 in 9 min, surpassing the thus far reported LIBs.

Fluorine atoms incorporation strengthens the strong metal-support interaction of PtNi@NFGC for enhanced methanol oxidation reaction performance under alkaline media

The regulatory mechanism of strong metal-support interaction (SMSI) is of great significance in improving the electrocatalytic performance for supported electrocatalysts. Here, PtNi alloy nanoparticles were deposited on N, F-codoped graphene-like carbon nanosheets (PtNi@NFGC) to construct a highly active interface for efficient methanol oxidation reaction (MOR), which solves the problems of high cost, poor activity and easy aggregation of Pt-based catalysts. Due to the high electrophilicity, F atoms doping into the carbon lattice can not only manipulate the electron structure and the state of the carbon skeleton, but also further trigger the stronger charge transfer between metal atoms and carbon support. Compared with single-doped PtNi@NGC, N, F-codoped PtNi@NFGC possesses a lower onset potential and methanol oxidation potential, higher methanol oxidation current and stronger CO tolerance. The results of the partial density of state (PDOS) simulation display that N, F-codoping promotes the electron transfer from Pt atoms to NFGC support, and leads to the d-band center shift upward, thus strengthening the oxidation degree of Pt active sites and increasing the composition of high-valent Ptx+. In-situ Raman analysis and density functional theory (DFT) results expound that F atoms embedding observably enhances the adsorption energy of Pt active centers to *OH intermediates, which not only significantly improves MOR catalytic activity, but also achieves efficient methanol dehydrogenation and alleviates CO poisoning. This customization of metal-support interface interaction by heteroatom doping strategy opens up opportunities for designing efficient supported catalysts.

Role of Heteroatom Doping in Enhancing the Catalytic Activities and Stability of Atomically Dispersed Metal Catalysts for Oxygen Evolution Reaction

Role of Heteroatom Doping in Enhancing the Catalytic Activities and Stability of Atomically Dispersed Metal Catalysts for Oxygen Evolution Reaction

Preparation of nitrogen-doped reduced graphene oxide/zinc ferrite@nitrogen-doped carbon composite for broadband and highly efficient electromagnetic wave absorption

Traditionally reduced graphene oxide (RGO)-based electromagnetic wave (EMW) absorbing materials have poor absorption effectiveness due to impedance mismatch caused by skin effect. The introduction of structural defects and the design of heterogeneous interfaces play a crucial role in enhancing the polarization effect of EMW absorbers. In this study, nitrogen-doped reduced graphene oxide/zinc ferrite@nitrogen-doped carbon (NRGO/ZnFe2O4@NC) ternary composite with rich heterogeneous interfaces is constructed by combining solvothermal reaction, in-situ polymerization, annealing treatment with subsequent hydrothermal reaction. The research results have shown that the obtained NRGO/ZnFe2O4@NC ternary composite exhibits a unique core-shell structure and excellent EMW absorption performance. At a thickness of 2.61 mm, the maximum effective absorption bandwidth can reach 7.2 GHz, spanning the entire Ku-band and a portion of the X-band, and the minimum reflection loss is –61.1 dB, which is superior to most reported RGO-based EMW absorbers. The excellent EMW absorbing ability is mainly ascribed to the optimized impedance matching and the enhanced polarization loss caused by the abundant heterogeneous interfaces and structural defects derived from heteroatomic nitrogen doping. Furthermore, the radar cross section in the far field is simulated by a computer simulation technique. This study provides a novel way to prepare core-shell magnetic carbon composites as highly efficient and broadband EMW absorbers.

The Surface/Interface Modulation of Platinum Group Metal (PGM)-Free Catalysts for VOCs and CO Catalytic Oxidation.

Effective management of volatile organic compounds (VOCs) and carbon monoxide (CO) is critical to human health and the ecological environment. Catalytic oxidation is one of the most promising technologies for achieving efficient VOCs and CO emission control. Platinum group metal (PGM)-free catalysts are recently receiving sustainable attention in catalyzing VOCs and CO removal due to their low cost, superior catalytic activity, and excellent stability, but PGM-free catalysts face challenges in low-temperature catalytic efficiency. In this mini-review, starting with discussing the catalytic mechanism of VOCs and CO oxidation, we summarize the surface/interface modulation strategies of PGM-free catalysts to promote oxygen and VOCs/CO molecule activation for enhanced low-temperature oxidation activity, including oxygen vacancy engineering, heteroatom doping, surface acidity modification, and active interface construction. We highlight the currently remaining challenges and prospects of advanced PGM-free catalyst development for highly efficient VOCs and CO emission control in practical applications.