Heteroatom Doping Research Articles

Enhanced carbon host with N-reinforced S-sites to catalyze rapid iodine conversion kinetics for Zn-I2 battery

Aqueous zinc-iodine (Zn-I2) battery is a promising energy storage system in the establishment of a low-carbon, clean society, but they are limited by unsatisfied reversible capacity and poor cycle life. Ultimately, this is due to the poor iodine conversion kinetics and the shuttle effect of the intermediate polyiodide. Herein, a N-reinforced S-site carbon host (labeled as NS-YP80F) is designed to resolve these issues. DFT calculation shows that the electrochemical activity of the NS-YP80F with abundant S-site can be further enhanced by introducing N-atom at the original S-site. The synergistic effect of N-reinforced S-site carbon host cannot only enhance the adsorption of polyiodide to avoid the shuttle effect, but also induce the smooth conversion of iodine through enhanced catalytic mechanism. Consequently, the Zn-I2 battery with NS-YP80F@I2 cathode shows high reversible capacity (127 mAh g−1 at 1C) and stable cycling lifespan (15,000 cycles) with a high current density of 50 C. This strategy achieved a breakthrough in the electrochemical activity of the heteroatom doping carbon hosts, and provided a simple and effective solution for optimizing the performance of Zn-I2 battery.

Electrochemical Switching of Electromagnetism by Hierarchical Disorder Tailored Atomic Scale Polarization.

High-frequency electronic response governs a broad spectrum of electromagnetic applications from radiation protection, and signal compatibility, to energy recovery. Despite various efforts to manage electric conductivity, dynamic control over dielectric polarization for real-time electromagnetic modulation remains a notable challenge. Herein, an electrochemical lithiation-driven hierarchical disordering strategy is demonstrated for actively modulating electromagnetic properties. The controllable formation and diffusion of coherent interfaces and cation vacancies tailor the coupling of atomic electric field and thus the locally polarized domains, which leads to the reversible electromagnetic transparency/absorption switching with a tunable range of -0.8--20.4 dB for the reflection loss and a broad operation bandwidth of 4.6 GHz. Compared to traditional methods of heteroatomic doping, hydrogenation, mechanical deformation, and phase transition, the electrochemical strategy shows a larger regulation scope of dielectric permittivity with the maximum increase ratios of 260% and 1950% for real and imaginary parts, respectively. This enables the construction of various device architectures including the adaptive window and pixelated metasurface. The results offer opportunities to achieve intelligent electromagnetic devices and pave an avenue to rejuvenate various electromagnetic functions of semiconductive oxides.

Copper-induced lattice distortion in Na4Fe3(PO4)2(P2O7) cathode enabling high power density Na-ion batteries with good cycling stability

Na4Fe3(PO4)2P2O7 (NFPP) has attracted attention due to its high theoretical capacity, low cost, and good structure stability for Na-ion batteries. However, its practical application is limited by the low intrinsic electronic conductivity and sluggish ion diffusion kinetics. To tackle those problems, lattice strain engineering by heteroatom doping is applied to tune the local molecular structure and optimize the electrochemical properties of electrode materials. Copper cation (+2) with a smaller ionic radius was chosen to dope at Fe-site in NFPP, and the doping amount was also optimized, illustrating the optimized sample of Na4Fe2.7Cu0.3(PO4)2P2O7 (NFPP-0.3Cu) delivered a high capacity of 119.01 mAh g-1 at 1C (1 C = 129 mA g-1) and a high capacity retention of 82.76% after 3000 cycles at 20 C. Notably, full cells with NFPP-0.3Cu as cathode and hard carbon as anode delivered a high energy density of 230 Wh kg-1 and a power density of 2280 W kg-1. The exceptional electrochemical performances are attributed to the modulated electronic structure and abundant lattice defects by Cu-doping. Furthermore, in-situ X-ray diffraction technique and theoretical calculation have jointly proved that the lattice distortions originated from Cu-doping have reduced the band gap of the NFPP-0.3Cu and altered the coordination environment of Fe, shortening the Fe-O and Cu-O bond lengths, significantly enhancing the intrinsic ionic conductivity and the diffusion kinetics of Na+. This work provides new point of views on lattice strain engineering and reaction kinetics of cathode materials in promoting high energy and power density sodium-ion batteries.

One-step pyrolysis derived Fe and heteroatom co-doped biochar composites for efficient microwave absorption

Electromagnetic (EM) pollution frequently disrupts the regular operation of sophisticated electrical devices, necessitating the urgent development of lightweight EM wave absorbers that possess powerful absorption capability. Herein, we report a simple method for the preparation of Fe and heteroatom co-doped biochar composites (FeX-BC, where X = N, S) by directly carbonizing the precursors of anhydrous FeCl3, cherry kernel powder, and heteroatom dopants (melamine or Na2S2O3·5H2O). By adding different amounts of dopants during the synthesis of the precursors, it is possible to adjust the heteroatom content of the FeX-BC samples with precision. It is worth mentioning that the FeN0.1-BC composite delivers the best EM wave absorption performance with an effective absorption bandwidth of 4.8 GHz and a minimal reflection loss of −63.2 dB. Furthermore, the significant attenuation of EM wave can be attributed to the synergistic interplay of magnetic loss, dielectric loss and the enhanced impedance matching. This study introduces a simple methodology for the fabrication of EM wave absorbers, a significant contribution to the synthesis, advancement, and functional applications of biomass-derived materials.

Development of an efficient bifunctional electrocatalyst based on Co/CoSe2 nanoparticles embedded in N, Se co-doped carbon for AEMFC and rechargeable Zn-air battery

We suggest a hollow-structured N, Se dual-doped carbon framework embedded with Co/CoSe2 nanoparticles (Co/CoSe2@NSeC) as highly efficient bifunctional electrocatalyst for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). The prepared electrocatalyst exhibits high electrochemical active surface area attributed to its unique hollow/porous structure and defective heteroatom doping sites. Furthermore, the strongly coupled heterojunction between Co and CoSe2 species not only provides abundant and highly active sites but also generates built-in electric field, thereby promoting electron transfer during the electrocatalytic reaction. Based on the above considerations, the prepared catalyst shows excellent bifunctional electrocatalytic performance. Leveraging the excellent ORR activity of Co/CoSe2@NSeC, alkaline exchange membrane fuel cells (AEMFC) with the Co/CoSe2@NSeC as air cathode exhibits high power density of 171.23 mW cm2. Furthermore, the rechargeable Zn-air battery employing the Co/CoSe2@NSeC shows high specific capacity (729.4 mAh gZn−1), peak power density (192.88 mW cm2), and sustained stability over 300 cycles.

Se-functionalized metal-free catalysts rich in sp3-hybridized carbon enable efficient oxygen electroreduction

Carbon-based metal-free materials are emerging as leading candidates to replace noble-metal catalysts in the oxygen reduction reaction (ORR). Herein, we introduce a facile secondary carbonation technique for fabricating Se and N co-doped metal-free catalysts using a zeolite imidazole framework (ZIF-8) as the precursor. The optimal electrocatalyst, designated SeNC-900, exhibited good ORR performance under both alkaline and acidic conditions, with half-wave potentials of 0.864 V and 0.731 V (vs. RHE), respectively. Density functional theory (DFT) calculations reveal that the enhanced activity of SeNC-900 originates from Se doping, which triggers an increase in the intrinsic defects of sp3-hybridized C. Concurrently, the sp3-hybridized C, in concert with Se dopant, modulates the electronic structure of the active C atoms. This work not only underscores the significance of tuning the electronic structure to boost catalytic performance by enriching intrinsic defects but also presents a fresh insight into the effect of heteroatom doping on carbon-based materials for electrocatalysis.

Supercapacitive behaviors of N/S co-doped biomass porous carbon-based supercapacitors in “water-in-salt” electrolyte

The design of carbon electrode materials and electrolytes is distinct significance for improving the energy density of supercapacitors. Herein, N/S co-doped biomass porous carbon materials based on sustainable resource were prepared by in-situ expansion, heteroatom doping, and subsequent KOH activation strategy by using camellia seed shell as carbon source and ammonium persulfate as dopant and expander. The as-prepared N/S co-doped biomass porous carbon (N/S-CSAC-650) possesses the characteristics of high specific surface area, large pore volume, and suitable heteroatom content. The N/S-CSAC-650 electrode achieves a high specific capacitance of 335.9 F g−1 in the 3 M KOH electrolyte at 0.5 A g−1. The constructed symmetric supercapacitor demonstrates excellent cyclic stability and shows a high retention rate of 98.4 % after 30,000 charge and discharge processes at 2 A g−1. Especially, the energy density of supercapacitors is usually constrained by the narrow electrochemical stability window (ESW) of dilute aqueous solution (1.23 V), in order to effectively widen the ESW of water, herein the “water-in-salt” (WIS) electrolyte strategy is put forward and the ESW of water was extended to 2.94 V by using a 25 M KAc WIS electrolyte. The operating voltage window of the symmetric supercapacitor assembled by 25 M KAc WIS electrolyte and N/S-CSAC-650 electrodes can reach 2.0 V, and a high energy density of 48.86 Wh kg−1 is realized.

Defect-rich hard carbon designed by heteroatom escape assists sodium storage performance for sodium-ion batteries

Sodium-ion batteries (SIBs) avoids the use of expensive cobalt element, and the abundance of sodium element is high, so it shows great application potential, and the development of sodium-ion battery materials is of great value. Biomass precursors have the advantages of low cost and widely and sufficiently distributed resources, and embody the environmental concept of waste utilization, however, the poor reversible specific capacity and initial coulombic efficiency (ICE) of pristine corn stover-derived hard carbons (CSHCs) limit their practical application value. In this paper, we propose a method to increase the reversible specific capacity of hard carbon and maintain high ICE, introduce heteroatoms into graphene-like nanosheets at low carbonization temperature, then escape heteroatoms through high pyrolysis temperature, create defects in the graphene-like carbon layer and expand the (002) layer spacing. Density functional theory (DFT) calculations show that defects are beneficial to the adsorption of Na+ on graphene-like nanosheets, and Na+ have a lower diffusion barrier between layers rich in defects and extended (002) layer spacing. Compared with the conventional low pyrolysis temperature heteroatom doping process, the present method exhibits superior ICE. In the ester-based electrolyte, the modified hard carbon (D-CSHC) exhibits a superior specific capacity of 284.5 mAh/g and an ICE of 85.9 % as compared to the pristine corn stover-derived hard carbon (233.5 mAh/g, 72.7 %). In addition, the capacity retention rate was 92.6 % after 500 turns of constant current cycles at 0.15 A/g.

In-situ ‘X’ doped ‘GCN’ photocatalyst enables selective aldehyde synthesis via photo-oxidation of benzyl alcohol under ambient conditions

Photo-oxidative selective conversion of benzyl alcohols using graphitic carbon nitride (GCN) is a sustainable strategy for conventional metal-doped heterogeneous catalytic oxidation systems. Non-metal doped graphitic carbon nitride (a subclass of GCN) enhances its properties as an efficient photocatalyst for oxidation. These heteroatom non-metal dopants alter the optical energy gap and chemical and electronic properties of GCN, making it ideal for creating cost-effective, practical utility. So, herein, we designed heteroatoms (X = B, S, C) doped GCN photocatalysts derived from melamine (M) with different heteroatom ingredients and compared their activity in detail. Among these, the photo-oxidation of benzyl alcohol under blue LED by S-doped GCN (S-GCN) photocatalyst exhibits utmost higher photocatalytic activity than other heteroatoms doped GCN photocatalyst due to suitable band gap and slow photoinduced charge carriers recombination. The suitable energy gap with higher chemical stability is accountable for the substantial increase in the photocatalytic efficiency of S-GCN in the solar light responsive integrating reactions of oxidation of benzyl alcohol in aerobic conditions. Attaining an exceptional >99 % selectivity towards benzaldehyde (up to 5 cycles without significant loss of activity) marks a remarkable milestone. This opens up new possibilities for using these simple non-metal-doped photocatalysts in fine chemical synthesis.

Crystal-dependent doping effects over MnO2 for Fenton-like catalysis optimization

Heteroatom doping is one of the most important strategies to improve the Fenton-like activity of heterogenous catalysts by optimizing the coordination environment and electronic structure of active sites. However, the doping effect on the crystal structure that governs the atom orientation and chemical stability of catalysts remains largely elusive. Here, we report the rational design and synthesis of a series of fluorine-doped MnO2 catalysts with different crystal phases (denoted as F-α-, F-β-, F-γ-, and F-δ-MnO2), aiming to reveal the crystal-dependent disparity of doping effects in PMS activation. Results demonstrate that fluorine doping exhibits selectivity towards specific crystal structures of MnO2 catalyst. The γ-MnO2 with a lowest Mn average oxidation state (AOS) significantly enhances the adsorption and activation of PMS upon fluorine doping, outperforming other MnO2 counterparts (i.e., α, β, and δ-type). Interestingly, we identify a strong linear correlation (R2 = 0.99) between the degradation rate constant variation (Δk) and ΔAOS divergence of MnO2 catalysts before and after fluorine doping, revealing a novel structure–activity relationship for Fenton-like catalysis optimization. In addition, a nonradical pathway with synergism of 1O2 and active surface-complex contributes greatly to pollutant removal in the developed F-γ-MnO2/PMS system, thereby demonstrating outstanding degradation performance towards electron-rich organics. This work provides fundamental insights into the crystal structure–activity relationship in the disparity of doping effect, which may inspire the rational design of efficient Fenton-like catalysts for wastewater treatment.

Ultrasound-assisted fungal self-growth and heteroatom doping for the preparation of high-performance lignocellulose-based supercapacitor electrodes

Biomass materials are widely used as supercapacitor electrode materials due to their cost-effectiveness and eco-friendliness. In this work, ultrasound-assisted impregnation was employed for the thorough mixing of the liquid medium, and fungal treatment was conducted on the three main components of lignocellulose to prepare a fungi-modified heteroatom-doped lignocellulose-based carbon material (LCF-NP). The effects of heteroatom doping, the content of the three main components, and fungal modification on the electrochemical performance of lignocellulose-based carbon materials was investigated. The results revealed the synergistic effect of heteroatom doping and fungal treatment on the electrochemical performance. Compared with its counterpart free of fungal treatment, LCF-NP has a more reasonable pore structure and exhibits excellent electrochemical performance. LCF-NP porous carbon material has the highest specific surface area (792 m2/g), large pore volume (0.523 cm3/g), and ideal specific capacitance (1940 mF/cm2) under the conditions of 1.0 M Na2SO4 electrolyte and current density of 0.5 mA/cm2. After 10,000 cycles, there is almost no loss of capacitance. These results indicate that the joint utilization of heteroatom doping and fungal treatment has a promising application prospect in pore structure regulation and electrochemical performance improvement. This study provides a new strategy for the preparation of lignocellulose-based carbon electrode materials.

MOF derived ZnCo2O4@nitrogen-doped carbon as an electrochemical sensor for simultaneous detection of acetaminophen and p-aminophenol

In this study, a rapid and sensitive electrochemical sensor (ZnCo2O4@NC) based on metal-organic frame (MOF)-derived metal oxide material (ZnCo2O4) and chitosan derived nitrogen-doped carbon material (NC) was successfully constructed for the simultaneous determination of acetaminophen (APAP) and p-aminophenol (PAP). A series of electrochemical experiments proved that the MOF derived ZnCo2O4@NC composite has excellent electrochemical response to APAP and PAP in the phosphate buffer saline (PBS) (pH 7.0). The current response varies linearly with the increase of APAP concentration in the range of 8.0 μmol L−1 to 520 μmol L−1 and PAP concentration in the range of 6.0 μmol L−1 to 420 μmol L−1. The sensitivity and limit of detection (LOD) of ZnCo2O4@NC for APAP and PAP detection are 0.1024 and 0.2749 μA μmol L−1 cm−2, 0.0608 and 0.2489 μmol L−1, respectively. The ZnCo2O4@NC composite modified electrode exhibits good selectivity, reproducibility and stability. Additionally, in the detection for acetaminophen sustained-release tablets, the recovery rates of APAP are in the range of 90.00 % –100.00 %. The theoretical content is consistent with our detection results, showing that this method has good accuracy in actual sample analysis. This study provides an innovative idea to improve electrochemical performance of simultaneous detection of acetaminophen and p-aminophenol through the comprehensive strategy of structural design, heteroatom doping.

Phosphorus heteroatom doped BiOCl as efficient catalyst for photo-piezocatalytic degradation of organic pollutant and unveiling the mechanism: Experiment and DFT calculation

A novel phosphorus heteroatom doped bismuth oxychloride (P-BiOCl) catalyst was synthesized and the photo-piezocatalytic degradation of rhodamine B dye performances were explored under the ultrasound vibration and light illumination. The P-BiOCl exhibited excellent photo-piezocatalytic degradation activity, such as an ultra-high reaction kinetic rate constant of 0.3961 min−1, efficient degradation efficiency (94.7 % within 8 min) and excellent stability compared to solely piezocatalysis and photocatalysis. More impressively, these outstanding performances of P-BiOCl exceeded pure BiOCl and most other catalytic materials systems. The relevant experimental and density functional theory (DFT) calculation results were exhibited to clarify enhanced photo-piezocatalytic mechanism. The introduction of P heteroatom could reduce the bandgap of BiOCl, modulate electronic structure and charge redistribution, provide novel electron channel to promote electron transfer and restrain charge carriers recombination. Additionally, P-doped could also enhance the adsorption of oxygen and water molecules, promote intrinsic catalytic activity, leading to the increased production of active free radicals ·O2– and ·OH, thus significantly boosting the efficiency of organic pollutant degradation. This work provides a comprehensive understanding of heteroatom doping enhancing photo-piezocatalytic activity and presents a potential new strategy for designing highly efficient catalysts for wastewater treatment.

Codoped germanene with 3p and 4p elements elements.

The relentless need for new materials to be used in electronic devices has opened new research directions in materials science. One of them involves using two-dimensional materials, among which there is current interest in using germanene. The heteroatom doping of germanene has been proposed as a possible approach to fine-tuning its electronic properties. However, this procedure is complicated because locating the dopants with a specific arrangement is challenging, thus achieving reproducibility. To avoid this problem, we propose the codoping of germanene to understand if dopants prefer to be agglomerated as observed for graphene or if they prefer to adopt a random disposition. Herein, we employed first-principles calculations to study 21 codoped germanene systems with one 3p (Al, Si, P, and S) and one 4p (Ga, As, and Se) element. Our results indicate that in the cases of AlP, AlS, GaP, GaS, GaAs, and GaSe codoped germanene, the dopants show a tendency to be located in specific lattice positions. The ortho disposition of dopants is preferred for AlP, AlS, GaP and GaS codoped germanene and their 4p counterparts GaAs and GaSe codoped germanene, and the materials showed interesting electronic propertiesmaking them suitable to develop germanene-based electronic materials. We utilized the M06-L, HSE06 methods accompanied by the 6-31G* basis sets to perform periodic boundary conditions calculations as implemented in Gaussian 09. The unit cells were sampled employing 100k-points for geometry optimizations and 2000k-points for electronic properties The ultrafine grid was employed. Results were visualized employing Gaussview 5.0.1. In addition to this, we performed B3LYP-D3 periodic calculations as implemented in CRYSTAL17.

Catalytic Decomposition of Residual Hydrogen Peroxide in N-Methylmorpholine-N-oxide by Heteroatom Doping Modified Activated Carbon

N-methyloxymoroline-N-oxide (NMMO) has been used in large quantities for the production of new solvent-treated cellulose. But, excess H2O2 used in the synthesis of NMMO from N-methylmorpholine (NMM) can adversely affect the quality of the product. This study introduces a novel approach using nitrogen and sulfur co-doped activated carbon (N,S co-doped AC) to catalyze the decomposition of residual H2O2 in NMMO products. Characterization techniques including N2 adsorption/desorption, Raman, TEM, FT-IR, and XPS were used to study the surface properties and chemistry of activated carbon doped with heteroatoms. The results revealed that AC800NS800 (800 is the calcinate temperature, NS is denoted by the co-doped of N and S) exhibited superior catalytic performance for H2O2 decomposition compared to singly doped activated carbons. Notably, over 95% of H2O2 in NMMO was decomposed, which the catalytic efficiency of AC800NS800 is no significant loss after ten times reuse. The exceptional catalytic activity of AC800NS800 is attributed to the presence of various functional groups on the surface (graphitic carbon, graphitic nitrogen, and pyrrole nitrogen). EPR tests identified HO• and O2•− as the primary reactive species in the H2O2 decomposition process. This study provides valuable insights into the catalytic decomposition of H2O2 in NMMO solutions and offers a significant reference for the production of high-quality NMMO.

Quasi-One-Dimensional Zigzag Covalent Organic Frameworks for Photocatalytic Hydrogen Evolution from Water.

Covalent organic frameworks (COFs) have potential applications in a wide range of fields. However, it remains a critical challenge to constrain their covalent expansions in the one-dimensional (1D) direction. Here, we developed a general approach to fabricate 15 different highly crystalline COFs with zigzag-packed 1D porous organic chains through the condensation of V-shaped ditopic linkers and X-shaped tetratopic knots. Appropriate geometrical combinations of a wide scope of linkers and knots with distinct aromatic cores, linkages, and functionalities offer a series of quasi-1D COFs with dominant pore sizes of 7-13 Å and surface areas of 116-784 m2 g-1. Among them, nitrogen (N)-doped 1D COFs with site-specific doping of heteroatoms favor a tunable control of band structures and conjugations and thus allow a remarkable hydrogen evolution rate up to 80 mmol g-1 h-1 in photocatalytic water splitting. This general strategy toward programming function in porous crystalline materials has the potential to tune the topologically well-defined electronic properties through precisely periodic doping.

Electronic Structure Regulated Carbon-Based Single-Atom Catalysts for Highly Efficient and Stable Electrocatalysis.

Single-atom-catalysts (SACs) with atomically dispersed sites on carbon substrates have attained great advancements in electrocatalysis regarding maximum atomic utilization, unique chemical properties, and high catalytic performance. Precisely regulating the electronic structure of single-atom sites offers a rational strategy to optimize reaction processes associated with the activation of reactive intermediates with enhanced electrocatalytic activities of SACs. Although several approaches are proposed in terms of charge transfer, band structure, orbital occupancy, and the spin state, the principles for how electronic structure controls the intrinsic electrocatalytic activity of SACs have not been sufficiently investigated. Herein, strategies for regulating the electronic structure of carbon-based SACs are first summarized, including nonmetal heteroatom doping, coordination number regulating, defect engineering, strain designing, and dual-metal-sites scheming. Second, the impacts of electronic structure on the activation behaviors of reactive intermediates and the electrocatalytic activities of water splitting, oxygen reduction reaction, and CO2/N2 electroreduction reactions are thoroughly discussed. The electronic structure-performance relationships are meticulously understood by combining key characterization techniques with density functional theory (DFT)calculations. Finally, a conclusion of this paper and insights into the challenges and future prospects in this field are proposed. This review highlights the understanding of electronic structure-correlated electrocatalytic activity for SACs and guides their progress in electrochemical applications.

High Capacitive Performance of N,O-Codoped Carbon Aerogels Synthesized via a One-Step Chemical Blowing and In Situ Activation Process.

Biomass and its derivatives, with their renewable characteristics, cost-effectiveness, and controllable structural and compositional properties, are promising precursors for carbon materials. Herein, N,O-codoped carbon aerogels were synthesized by carbonization and zinc nitrate activation of histidine. The specific surface area (SSA) was markedly increased with the addition of zinc nitrate, and the maximum value achieved 853 m2 g-1 for ZHC-11 obtained with the molar ratio of 1:1 between histidine and zinc nitrate. The D/G-band intensity ratio increased from 1.55 for the histidine-derived control sample HC to 1.65 for ZHC-11, indicating the enhancement of amorphous feature. The nitrogen content increased from 6.5% for HC to 1.60 for ZHC-11. The optimized microstructure and enriched heteroatom doping are beneficial to the capacitance performance. The optimum electrode exhibited 234.1 F g-1 at 0.1 A g-1 and maintained 116.5 F g-1 at 60 A g-1 in a three-electrode system. In particular, the symmetric supercapacitor showed 121.9 F g-1 and 19.5 Wh kg-1 at 0.2 A g-1. This research offers guidance on the cost-effective synthesis of carbon materials for supercapacitors, while also providing novel insights to realize the complete utilization of biomass derivatives.

Bimolecular Salt Strategy Enhances Heteroatom Doping and Porosity Optimization of Porous Carbon for Supercapacitors.

The incompatibility between electrolyte ions and electrode pore sizes, coupled with the extensive use of activators and dopants, significantly restricts the fabrication of porous carbon materials. Consequently, developing environmentally sustainable and efficient methodologies that exploit the intrinsic properties and pretreatment of materials to facilitate self-activation and self-doping becomes crucial. In this study, potassium histidine and magnesium histidine molecular salts were synthesized as precursors, enabling specific ion activation and bimetallic template-directed tunable porosity through a one-step carbonization process. Notably, the ratio of bimolecular salts significantly influenced the porous structure of carbon, the properties of heteroatoms, and the electrochemical performance. By optimizing the ratio, the porous carbon materials exhibited high accessibility to electrolyte ions and effective ion/electron transport channels. Consequently, the optimal sample (NOSPC-2) achieved a high specific capacitance of 318 F g-1 at 0.1 A g-1 and a good capacitance retention rate of 98.8% after 50,000 cycles at 5 A g-1. In addition, NOSPC-2 also boasted high energy density and power density, reaching 22 Wh kg-1 and 25 kW kg-1, respectively. This research represents a significant stride in advancing preparation technologies for small molecule derived porous carbon materials, providing valuable insights for the rational design of carbon electrode materials for capacitive energy storage.

Carbon Dots in Photodynamic Therapy: The Role of Dopant and Solvent on Optical and Photo-Responsive Properties.

Carbon dots (CDs) are novel carbon-based luminescent materials with wide-ranging applications in biosensing, bioimaging, drug transportation, optical devices, and beyond. Their advantageous attributes, including biocompatibility, biodegradability, antioxidant activity, photostability, small particle size (<10 nm), and strong light absorption and excitation across a broad range of wavelengths, making them promising candidates in the field of photodynamic therapy (PDT) as photosensitizers (PSs). Further enhancements in functionality are imperative to enhance the effectiveness of CDs in PDT applications, notwithstanding their inherent benefits. Recently, doping agents and solvents have been demonstrated to improve CDs' optical properties, solubility, cytotoxicity, and organelle targeting efficiency. These improvements result from modifications to the CDs' carbon skeleton matrices, functional groups on the surface state, and chemical structures. This review discusses the modification of CDs with heteroatom dopants, dye dopants, and solvents to improve their physicochemical and optical properties for PDT applications. The correlations between the surface chemistry, functional groups, the structure of the CDs, and their optical characteristics toward quantum yield, redshift feature, and reactive oxygen species (ROS) generation, have also been discussed. Finally, the progressive trends for the use of CDs in PDT applications are also addressed in this review.