Heteroatom-doped Carbon Research Articles

Pulsed Laser Manufactured Heteroatom Doped Carbon Dots via Heterocyclic Aromatic Hydrocarbons for Improved Tribology Performance.

Traditional laser-assisted method (top-down synthesis strategy) is applied in the preparation of carbon dots (CDs) by cutting larger carbon materials, which requires harsh conditions, and the size distribution of the CDs is seldom monodisperse. In this work, heteroatom-doped CDs, represented by N,S co-doped CDs (N,S-CDs), can be prepared successfully by pulsed laser irradiation of heterocyclic aromatic hydrocarbons-based small molecule compound solution. The friction coefficient (COF) of base oil PAO decreases from 0.650 to 0.093, and the wear volume reduces by 92.0% accompanied by 1 wt.% N,S-CDs addition, while the load-bearing capacity is improved from 100 to 950 N. The excellent lubrication performance is mainly attributed to the formation of a robust tribofilm via a tribochemical reaction between N,S-CDs and friction pairs, and the N,S-CDs can play a mending effect and polishing effect for worn surfaces. Furthermore, the lubricant containing heteroatom doped CDs are capable of being prepared in situ via pulsed laser irradiation of heterocyclic aromatic hydrocarbons in base oil, which can avoid the redispersed problem of nano-additive in base oil to maintain long-term dispersion, with COF of 0.103 and low wear volume ≈1.99 × 105 µm3 (76.9% reduction) even after standing for 9 months.

Research Experiences via Integrating Simulations and Experiments (REVISE): A Model Collaborative Research Project for Undergraduate Students in CO2 Sorbent Design.

Undergraduate research experiences are an instrumental component of student development, increasing conceptual understanding, promoting inquiry-based learning, and guiding potential career aspirations. Moving one step further, as research continues to become more interdisciplinary, there exists potential to accelerate student growth by granting additional perspectives through collaborative research. This study demonstrates the utilization of a model collaborative research project, specifically investigating the development of sorbent technologies for efficient CO2 capture, which is an important research area for improving environmental sustainability. A model CO2 sorbent system of heteroatom-doped porous carbon is utilized to enable students to gain knowledge of adsorption processes, through combined experimental and computational investigations and learnings. A particular emphasis is placed on creating interdisciplinary learning experiences, exemplified by using density functional theory (DFT) to understand molecular interactions between doped carbon surfaces and CO2 molecules as well as explain underlying physical mechanisms that govern experimental results. The experimental observations about CO2 sorption performance of doped ordered mesoporous carbons (OMCs) can be correlated with simulation results, which can explain how the presence of heteroatom functional groups impact the ability of porous carbon to selectively adsorb CO2 molecules. Through an inquiry-focused approach, students were observed to couple interdisciplinary results to construct holistic explanations, while developing skills in independent research and scientific communications. This collaborative research project allows students to obtain a deeper understanding of sustainability challenges, cultivate confidence in independent research, prepare for future career paths, and most importantly, be exposed to strategies employing interdisciplinary research approaches to address scientific challenges.

Heteroatom-doped porous carbon materials for high performance supercapacitors

Heteroatom-doped carbon materials have considerable potential for applications in energy storage devices (ESDs). In this study, an interconnected B/N/O/P co-doped porous carbon materials (B5-CPPCN-700) was synthesised using a simple one-step method with zinc nitrate hexahydrate and 4′-(4-phosphonylphenyl)−3,2′:6′,3″-terpyridine as raw materials through KOH activation. The as-prepared B5-CPPCN-700 had a large specific surface area, rough surface for ion adsorption, and suitable pore size distribution for electron transport. Moreover, the co-doped B/N/O/P species—particularly the B species—in B5-CPPCN-700 provided active sites and additional pseudocapacitance. These structural and morphological features ensured a high specific capacitance of 503.3 F/g at 0.5 A/g. Furthermore, the assembled symmetric supercapacitor delivered a satisfactory specific energy, specific power (14.98 Wh/kg at 300 W/kg and 6.97 Wh/kg at 22,800 W/kg), and specific capacitance (149.8 F/g at 0.5 A/g and 77.2 F/g at 40 A/g). This study paves the way for the preparation of high-capacitance porous carbon materials for ESDs.

Aerobically Autoxidized Self-Charge Concept Derived from Synergistic Pyrrolic Nitrogen and Catechol Configurations in N, O Co-Doped Carbon Cathode Material.

Aerobically autoxidized self-charging concept has drawn significant attraction due to its promising chemical charge features without external power supply. Particularly, heteroatom-doped carbon materials with abundant oxidizable sites and good conductivity are expected to be ideal cathode materials. However, there is no well-defined aerobically autoxidized self-charging concept based on heteroatom-doped carbon materials, significantly hindering the design of related carbon cathodes. An aerobically autoxidized self-chargeable concept derived from synergistic effect of pyrrolic nitrogen and catechol configuration in carbon cathode using model single pyrrolic nitrogen and oxygen (N-5, O) co-doped carbon and O-enriched carbon is proposed. First, self-charging of N-5, O co-doped carbon cathode can be achieved by aerobic oxidation of pyrrolic nitrogen and catechol to oxidized pyrrolic nitrogen and ortho-quinone configurations, respectively. Second, introducing a single pyrrolic nitrogen configuration enhanced acidic wettability of N-5, O co-doped carbon facilitating air self-charge/galvanic discharge involving proton removal/introduction. Third, synergistic effect of pyrrolic nitrogen and hydroxyl species with the strong electron-donating ability to conjugated carbon-based backbone endows N-5, O co-doped carbon with a higher highest occupied molecular orbital (HOMO) energy level more susceptible to oxidation charging. The assembled Cu/Carbon batteries can drive a timer after every air-charging run. This promising aerobically autoxidized self-charging concept can inspire exploring high-efficiency self-charging devices.

Discarded Perseaamericana leaf-derived natural O, Mg, and Ca self-doped activated carbon and its applications as electrode materials for high-performance symmetric supercapacitors

Recently, there has been growing research interest in the fabrication of heteroatom-doped porous carbon from biomass. Herein, natural O, Mg, and Ca self-doped activated carbon was fabricated from discarded Persea americanaleaves via a one-step route strategy. By varying the carbonization temperature (500, 600, 700, and 800 °C), the as-fabricated DPAL-AC exhibits a high surface area (875.775 m2/g) and rich natural O, Mg, and Ca heteroatoms composition. The symmetric device product (DPAL-AC700) exhibits a high gravimetric capacitance of 209 F/gat 1 A/g. In addition, the device delivered an energy density of 28.4 Wh/kg at a power density of 135.5 W/kg. This work presents a novel approach to producing self-doped activated carbon with natural heteroatoms, which can enhance the performance of symmetric supercapacitors.

Boosted hydrogen evolution kinetics of heteroatom-doped carbons with isolated Zn as an accelerant

Carbon-based single-atom catalysts, a promising candidate in electrocatalysis, offer insights into electron-donating effects of metal center on adjacent atoms. Herein, we present a practical strategy to rationally design a model catalyst with a single zinc (Zn) atom coordinated with nitrogen and sulfur atoms in a multilevel carbon matrix. The Zn site exhibits an atomic interface configuration of ZnN4S1, where Zn's electron injection effect enables thermal-neutral hydrogen adsorption on neighboring atoms, pushing the activity boundaries of carbon electrocatalysts toward electrochemical hydrogen evolution to an unprecedented level. Experimental and theoretical analyses confirm the low-barrier Volmer-Tafel mechanism of proton reduction, while the multishell hollow structures facilitate the hydrogen evolution even at high current intensities. This work provides insights for understanding the actual active species during hydrogen evolution reaction and paves the way for designing high-performance electrocatalysts.

Organic polymer coating induced multiple heteroatom-doped carbon framework confined Co1-xS@NPSC core-shell hexapod for advanced sodium/potassium ion batteries

Synthesis of advanced structure and multiple heteroatom-doped carbon based heterostructure materials are the key to the preparation of high-performance energy storage electrode materials. Herein, the hexapod-shaped Co1-xS@NPSC has been triumphantly prepared using hexapod ZIF-67 as the sacrificial template to prepare Co1-xS inner core and N, P, and S tri-doped carbon (NPSC) as the shell through the carbonization of the organic polymer precursor. When applied as anode for Na+ batteries (SIBs) and K+ batteries (PIBs), Co1-xS@NPSC presents the high reversible specific capability of 747.4 mAh/g at 1.0 A/g after 235 cycles and 387.8 mAh/g at 5.0 A/g after 760 cycles for SIBs, as well as 326.7 mAh/g at 1.0 A/g after 180 cycles for PIBs. The excellent storage capacity and rate capability of Co1-xS@NPSC is ascribed to hexapod structure of ZIF-67 unlike the common dodecahedron, which is constructed with interior porous and exterior framework repository, donating supplemental active sites, and doping of multiple heteroatoms forming organic polymer coating inhibiting the volume expansion and restrains the agglomeration of Co1-xS nanoparticles. This approach has paved a bright avenue to exploit promising anode materials with novel structure and hetero-atom doping for high-performance energy storage devices.

Fluoropyridine-medicated zeolite templating method for N/F co-doped carbon with high electrocatalytic performance on oxygen reduction reaction

Heteroatom-doped carbons have attracted increasing attention in recent years as inexpensive high-performance electrocatalytic materials owing to their electrical properties. A precisely controlled synthesis method for heteroatom-doped carbons is important to improve their performance and expand their applications. In this study, we developed a fluoropyridine-medicated zeolite templating method for Nitrogen/Fluorine (N/F) co-doped carbons. The N/F co-doped carbons showed better catalytic performances for oxygen reduction reaction (ORR) than N-doped carbon prepared using pyridine. In particular, the optimized N/F co-doped carbon exhibited a higher half-wave potential (0.87 V vs. RHE) than commercial Pt-loaded carbon black and N/F co-doped carbons reported in the literature. The comparative studies using various N/F co-doped carbons revealed that semi-ionic bonded C-F might improve ORR activity. In contrast, the contribution from covalent or ionic C-F to improving ORR activity would be negligible.

Bimetallic phosphide wrapped in hierarchically structured P, N co-doped porous carbon nanocatalysts for enhanced rechargeable Li[sbnd]O2 batteries

Recently, transition-metal phosphides (TMPs) cathode materials possess tremendous prospects for lithium‑oxygen batteries (LOBs). However, designing highly efficient TMPs cathode materials achieving long-cycling stability still faces numerous obstacles. The hierarchical porous carbon is expected to be a remarkable substrate for transition-metal composites because of its high specific surface area and superior electrical conductivity. Herein, NiCoP@PNC hybrid catalysts consisting of NiCoP nanoparticles and heteroatom-doped carbon skeleton were prepared via simple freeze-drying and high-temperature pyrolysis methods. The NiCoP@PNC composites with a high specific surface area and rich interior porosity can effectively accelerate charge transfer and enhance electrocatalytic activity. Compared with either Co2P@PNC and PNC electrodes, the NiCoP@PNC cathode delivers an enhanced specific capacity of 14,028.1 mAh g−1 at 100 mA g−1. The NiCoP@PNC catalytic LOBs can reach 196 cycles with the fixed capacities of 500 mAh g−1 at 200 mA g−1 due to the increased electron transfer efficiency and improved electrochemical reaction kinetics. This approach provides a facile method to prepare TMP-based composite materials for developing high-performance LOBs.

Chitosan-derived mesoporous N-doped carbon catalyst embedded with NiO for highly selective benzyl alcohol oxidation

MOF-derived heteroatom-doped mesoporous carbons have gained the significant consideration in heterogenous catalytic reactions because of their multipurpose features. Especially, the high Specific Surface Area (SSA) of these materials provides abundant activated sites for the catalytic reactions, while the mesoporous structure allows for the effective mass transfer, enhancing the overall capability of the catalytic process. Herein, the efficient NiO/CN-T (T referred to the pyrolysis temperature) was prepared by facile pyrolysis of MOF/CS composite (Ni-MOF (74), Chitosan) in the presence of excess amount of starch as the carbon precursor. The NiO/CN-T as heterogenous catalyst has desired SSA varied from 1094 to 491 m2.g−1. The optimized catalyst (NiO/CN-600) possesses the superior catalytic activity toward the oxidation of the BnOHs due to its high SSA (1094 m2.g−1), which can notably rectify the mass transfer proficiency. Additionally, the NiO/CN-600 heterogenous catalyst also represents the acceptable chemical stability. So, it was demonstrated that such an innovative strategy can provide several versatile tunability insights for the preparation of MOF/biopolymer-derived heterogenous catalysts.

Harnessing fluorescent carbon quantum dots from natural resource for advancing sweat latent fingerprint recognition with machine learning algorithms for enhanced human identification.

Nowadays, it is fascinating to engineer waste biomass into functional valuable nanomaterials. We investigate the production of hetero-atom doped carbon quantum dots (N-S@MCDs) to address the adaptability constraint in green precursors concerning the contents of the green precursors i.e., Tagetes erecta (marigold extract). The successful formation of N-S@MCDs as described has been validated by distinct analytical characterizations. As synthesized N-S@MCDs successfully incorporated on corn-starch powder, providing a nano-carbogenic fingerprint powder composition (N-S@MCDs/corn-starch phosphors). N-S@MCDs imparts astounding color-tunability which enables highly fluorescent fingerprint pattern developed on different non-porous surfaces along with immediate visual enhancement under UV-light, revealing a bright sharp fingerprint, along with long-time preservation of developed fingerprints. The creation and comparison of latent fingerprints (LFPs) are two key research in the recognition and detection of LFPs, respectively. In this work, developed fingerprints are regulated with an artificial intelligence program. The optimum sample has a very high degree of similarity with the standard control, as shown by the program's good matching score (86.94%) for the optimal sample. Hence, our results far outperform the benchmark attained using the conventional method, making the N-S@MCDs/corn-starch phosphors and the digital processing program suitable for use in real-world scenarios.

Dual heteroatom-doped biomass-derived porous carbon anode for superior sodium storage

The green preparation of anode materials is desirable for high-performance sodium-ion batteries. In this paper, a N/S co-doped porous carbon was prepared from longan shell via a facile and low-cost route. Heteroatom doping increases the defect sites to facilitate Na+ storage and improves the electronic conductivity of the carbon material. The N/S co-doped porous carbon prepared using CS(NH2)2 with a ratio of 1:2 displays the highest specific capacity of 314.7 mAh g−1 after 200 cycles at 0.1 A g−1. In addition, a reversible specific capacity of 202.5 mAh g−1 is maintained after 1000 cycles at 1 A g−1. This work offers a new strategy for designing high-performance anode materials for sodium energy storage applications.

Organic precursors for tailored synthesis of sulfur- and nitrogen-doped mesoporous carbons: a molecular design approach.

Insights into tailoring heteroatom-doped mesoporous carbon are provided for enhanced electrocatalytic properties. This study focuses on the design and synthesis of sulfur-doped mesoporous carbon using a sulfur-containing monomer with a chemical structure similar to dopamine. The resulting material achieves remarkable catalytic activity for the oxygen reduction reaction.

Heteroatom-doped lignin-derived carbon material: performance and application

This review summarizes the influence of heteroatom-doping on the physicochemical properties of lignin-based carbon, together with its electro-chemical property in batteries and capacitors and adsorption ability for the removal of pollutants.

Biomolecule-derived three-dimensional N, P co-doped carbon nanosheets for the efficient oxidative dehydrogenation of propane.

Non-metallic heteroatom-doped carbon materials are promising catalysts for the oxidative dehydrogenation of propane (ODHP), but their controlled synthesis remains challenging. Herein, a novel three-dimensional N, P co-doped carbon nanosheet (NPC-NS-T) catalyst is prepared, which shows an impressive catalytic performance in the ODHP reaction with high propane conversion (20.0%) and high selectivity for propene (62.1%) and olefins (64.5%) at 500 °C along with good long-time stability. Comprehensive experimental characterizations revealed that incorporation of appropriate P can not only help to form more CO species on the surface of NPC-NS-T but also inhibit the consumption of CO species under ODHP conditions, thereby remarkably improving the catalytic performance. This work could pave the way for developing efficient biomass-derived carbon catalysts for the oxidative dehydrogenation reactions of propane.

Cutting-edge nitrogen, boron, and fluorine triply doped chain-like porous carbon nanofibers: a versatile solution for high-performance zinc–air batteries and self-powered water splitting

Heteroatom-doped carbon catalysts are a class of materials that have been widely studied for their potential to improve the performance and kinetics of electrochemical reactions such as the oxygen reduction/evolution reaction (ORR/OER).

Research Progress on Electrocatalysts for Electrocatalytic Carbon Dioxide Reduction

Electrochemical CO2 reduction reaction (CO2RR) is a vital strategy for achieving carbon neutrality by converting CO2 into high-energy-density, valuable chemical products, thereby facilitating carbon resource recycling and addressing environmental challenges. Herein, this paper emphasizes the role of CO2RR in diminishing the greenhouse effect through the transformation of CO2, with a particular focus on the latest advancements in Cu-based nanocatalysts, metal-organic framework (MOF)-based catalysts, and heteroatom-doped carbon materials, which are key innovations in achieving enhanced photoelectric conversion efficiency and steering CO2 conversion pathways. The paper also outlines the electrochemical principles of CO2RR, and the spectrum of potential reduction products, and navigates through the challenges of stability and production costs. The paper proposes strategies to surmount these hurdles, highlighting the critical role of industrial collaborations and breakthroughs in materials science. Future research should aim to pinpoint cost-effective, efficient catalysts for CO2RR, contributing significantly to mitigating the greenhouse effect and propelling forward sustainable energy solutions.

Heteroatom-doped carbon nanomaterials as potential heterogeneous Fenton reaction catalysts

A volcano relationship between the catalytic activity and the adsorption energies of reaction intermediates was found for the H2O2 dissociation on heteroatom-doped carbon nanomaterials.

Synergism in carbon nanotubes and carbon-dots: counter electrode of a high-performance dye-sensitized solar cell.

Dye-sensitized solar cells (DSSCs) play a crucial role in the realm of renewable energy technology by converting solar energy into electrical energy in an efficient and cost-effective way. In the pursuit of improving the photoconversion efficiency (PCE) of DSSCs, this work aims at fabricating a new counter electrode (CE) using a binary composite of heteroatom-doped carbon dots (C-dots) and functionalized multi-walled carbon nanotubes (o-MWCNTs). We demonstrate that this binary composite exhibits superior performance to pristine o-MWCNTs, resulting in a remarkable enhancement in the PCE. The PCE of the o-MWCNT/C-dots composite was measured at an impressive 4.28%, significantly outperforming the pristine o-MWCNT electrode, which yielded an efficiency of 2.24%. The enhanced performance of the o-MWCNT/C-dots composite can be attributed to the synergistic effects of heteroatom-doped C-dots since their binding to the o-MWCNTs by activated oxygenic surface functional groups increases the surface area from 218 to 253 m2 g-1. This enhanced surface area results from the reduction of π-π stacking interactions of the individual tubes and production of a new hollow channel in the structure that provides an ideal scaffold for I2 adsorption and electron transfer. We demonstrate the role of C-dots on MWCNT's property modulation toward higher PCE by density functional theory (DFT) calculation and electrochemical analysis. Electron-excess N and S doped C-dots exhibit strong catalytic activity, allowing for rapid electron transfer processes in the CE-electrolyte surface via the donor acceptor mechanism, whereas electron-deficient B doped C-dots undermine the cell performance by forming a charge recombination trap at the CE surface. The synthesized composite has higher redox reversibility up to 100 CV cycles and chemical stability, studied by the post-performance material characterization. The findings offer a promising avenue for the development of high-performance DSSCs, which will help to promote sustainable and renewable energy technologies.

Heteroatom-doped and graphitization-enhanced lignin-derived hierarchically porous carbon via facile assembly of lignin-Fe coordination for high-voltage symmetric supercapacitors

Lignin-derived carbon materials are widely used as electrode materials for supercapacitors. However, the electrochemical performance of these materials is limited by the surface chemistry and pore structure characteristics. Herein, a novel and sustainable strategy was proposed to prepare heteroatom-doped lignin-derived carbon material (Fe-NLC) with well-developed pore size distributions and enhanced graphitization structure via a facile lignin-Fe coordination method followed by carbonization. During carbonization, Fe3+ in lignin-metal complexes evolve into nanoparticles, which act as templates to introduce porous structures in carbon materials. Also, the lignin-Fe coordination structure endows the material with a higher graphitization during carbonization, thereby improving the structural properties of the carbon materials. Due to the removal of Fe3O4 template, the obtained Fe-NLC possessed reasonable pore distribution and nitrigen/oxygen (N/O) functional groups, which can improve the wettability of materials and introduce pseudocapacitance. Accordingly, Fe-NLC possesses a notable specific capacitance of 264 F/g at 0.5 A/g. Furthermore, a symmetric supercapacitor Fe-NLC//Fe-NLC with a high voltage window (1.8 V) was constructed. The symmetric supercapacitor exhibits a maximum energy density of 15.97 Wh/kg at 450 W/kg, demonstrating well application prospects. This paper proposes a novel approach for preparing carbon materials via lignin-metal coordination to provide an alternative way to explore sustainable and low-cost energy storage materials.