Carbon Nanoribbons Research Articles

Investigating structural disparities in carbon nanoribbons and nanobelts through spectroscopies

Investigating structural disparities in carbon nanoribbons and nanobelts through spectroscopies

Origin of the Slope Capacity of Sodium-Ion Storage in Hydrogen-Rich Carbon Nanoribbon

Origin of the Slope Capacity of Sodium-Ion Storage in Hydrogen-Rich Carbon Nanoribbon

Efficient generation of 1O2 by activating peroxymonosulfate on graphitic carbon nanoribbons for water remediation

Few-layer graphitic carbon nanoribbons (GCN) with rich defective sites were prepared by pyrolysis at 800 oC in N2 of in situ-chelated Fe-polyaniline complexes synthesized via one-pot homogeneous Fenton-like oxidative polymerization of an acidic aniline solution. A minimal amount of iron (0.47 wt%) made a pivotal role in the nanoribbon growth and graphitization of GCN, and deposited highly dispersed iron species on GCN without post-synthesis acid leaching, which greatly simplified the synthesis procedure of GCN with improved yield. GCN exhibited high activity and stability for catalytic degradation of organic pollutants with peroxymonosulfate (PMS) mainly via non-radical pathways. The influences of various operating parameters on the catalytic performance of GCN were investigated. Scavenging tests, spin-trapping electron paramagnetic resonance spectra, electrochemical analyses, and theoretical calculations unveiled that 1O2 was the main reactive oxygen species generated from synergistic activation of PMS on GCN while GCN-mediated electron transfer made a minor contribution to organic degradation.

Theoretical Study on the Electrocatalytic CO2 Reduction Mechanism of Single-Atom Co Complexed Carbon-Based (Co-Nχ@C) Catalysts Supported on Carbon Nanotubes.

Electrocatalytic CO2 reduction serves as an effective strategy to tackle energy crises and mitigate greenhouse gas effects. The development of efficient and cost-effective electrocatalysts has been a research hotspot in the field. In this study, we designed four Co-doped single-atom catalysts (Co-Nχ@C) using carbon nanotubes as carriers, these catalysts included tri- and dicoordinated N-doped carbon nanoribbons, as well as tri- and dicoordinated N-doped graphene, respectively denoted as H3(H2)-Co/CNT and 3(2)-Co/CNT. The stable configurations of these Co-Nχ@C catalysts were optimized using the PBE+D3 method. Additionally, we explored the reaction mechanisms of these catalysts for the electrocatalytic reduction of CO2 into four C1 products, including CO, HCOOH, CH3OH and CH4, in detail. Upon comparing the limiting potentials (UL) across the Co-Nχ@C catalysts, the activity sequence for the electrocatalytic reduction of CO2 was H2-Co/CNT > 3-Co/CNT > H3-Co/CNT > 2-Co/CNT. Meanwhile, our investigation of the hydrogen evolution reaction (HER) with four catalysts elucidated the influence of acidic conditions on the electrocatalytic CO2 reduction process. Specifically, controlling the acidity of the solution was crucial when using the H3-Co/CNT and H2-Co/CNT catalysts, while the 3-Co/CNT and 2-Co/CNT catalysts were almost unaffected by the solution's acidity. We hope that our research will provide a theoretical foundation for designing more effective CO2 reduction electrocatalysts.

Investigation of column purified dye derived carbon nanomaterials for security printing and supercapacitor applications

Literature evidence reveals versatile applications of carbon dots (CDs), but generally mixtures of various types of carbon nanomaterials, molecular intermediates as well as side products are obtained upon hydrothermal treatment of the precursor material. This demands isolation of pure components and their complete characterization before these nano carbonaceous materials are chosen for suitable applications. In the present study, perylenetetracarboxylic dianhydride (PTCDA) is subjected to hydrothermal treatment and the mother liquor obtained is separated using column chromatography technique using dichloromethane-methanol solvent system to isolate fractions of various fluorescent carbonaceous nanostructures. The TEM imaging of nano carbonaceous particles of all five fractions indicated that the first and third fractions were composed of nanoribbons, while the latter two fractions largely contained quasi-spherical nanoparticles of both lesser (carbon quantum dots) and greater (carbon nanodots) than 10 nm dimensions. The XPS results of all the fractions suggested separation based on polarity difference. The ID/IG ratios obtained from Raman spectra implied the presence of several defects on the CDs. The time resolved fluorescence spectra of third, fourth and fifth fractions revealed mono-exponential decay of fluorophores with excitation independent average lifetime values. The fifth fraction exhibited good biocompatibility and the highest absolute fluorescence quantum yield of 58.47 % among all the isolated samples. As these CDs displayed a remarkable rise in the quantum yield to 88.60 % when dispersed in water, a water-based flexo-ink was formulated. The photostable pale yellow flexo print proofs obtained on UV dull paper exhibited a green fluorescence under 365 nm illumination, whereas a yellow glow when shined with blue light, which can serve as an authentication feature for security documents and currency notes. Moreover, as the third fraction constitutes mainly of carbon nanoribbons (CNRs), an optimized polymer electrolyte was prepared along with sodium alginate (SA), and MgCl2 to understand their potential use in energy storage application. A supercapacitor was fabricated and tested for its electrochemical performance such as cyclic voltammtery (CV), electrochemical impedance spectroscopy (EIS) and galvanostatic charge/discharge (GCD). An enhanced current window was observed in the CV of SA/CNRs compared to pure SA and SA/CNRs/Mg films, which indicated a structural interaction of CNRs with SA. The conductivity of SA/CNRs/Mg was lesser than SA/CNRs in EIS studies due to the presence of Mg ions, while pure SA showed lesser conductivity. The dual ionic interaction of Na and Mg along with enhanced structural stability due to doped CNRs favors its convenient supercapacitor application. The fabricated eco-friendly supercapacitor showed a specific capacitance of 84 F/g. The GCD of the device displayed pseudocapacitance behaviour and was quite stable for 2000 cycles with coulombic efficiency of 96 %.

Molecular Dynamics Study of Nanoribbon Formation by Encapsulating Cyclic Hydrocarbon Molecules inside Single-Walled Carbon Nanotube.

Carbon nanotubes filled with organic molecules can serve as chemical nanoreactors. Recent experimental results show that, by introducing cyclic hydrocarbon molecules inside carbon nanotubes, they can be transformed into nanoribbons or inner tubes, depending on the experimental conditions. In this paper, we present our results obtained as a continuation of our previous molecular dynamics simulation work. In our previous work, the initial geometry consisted of independent carbon atoms. Now, as an initial condition, we have placed different molecules inside a carbon nanotube (18,0): C5H5 (fragment of ferrocene), C5, C5+H2; C6H6 (benzene), C6, C6+H2; C20H12 (perylene); and C24H12 (coronene). The simulations were performed using the REBO-II potential of the LAMMPS software package, supplemented with a Lennard-Jones potential between the nanotube wall atoms and the inner atoms. The simulation proved difficult due to the slow dynamics of the H abstraction. However, with a slight modification of the parameterization, it was possible to model the formation of carbon nanoribbons inside the carbon nanotube.

Critical Role of Aromatic C(sp2)-H in Boosting Lithium-Ion Storage.

Exploring high-sloping-capacity carbons is of great significance in the development of high-power lithium-ion batteries/capacitors (LIBs/LICs). Herein, an ion-catalyzed self-template method is utilized to synthesize the hydrogen-rich carbon nanoribbon (HCNR), achieving high specific and rate capacity (1144.2/471.8 mAh g-1 at 0.1/2.5 A g-1). The Li+ storage mechanism of the HCNR is elucidated by in situ spectroscopic techniques. Intriguingly, the protonated aromatic sp2-hybridized carbon (C(sp2)-H) can provide additional active sites for Li+ uptake via reversible rehybridization to sp3-C, which is the origin of the high sloping capacity. The presence of this sloping feature suggests a highly capacitance-dominated storage process, characterized by rapid kinetics that facilitates superior rate performance. For practical usage, the HCNR-based LIC device can deliver high energy/power densities of 198.3 Wh kg-1/17.9 kW kg-1. This work offers mechanistic insights on the crucial role of aromatic C(sp2)-H in boosting Li+ storage and opens up new avenues to develop such sloping-type carbons for high-performance rechargeable batteries/capacitors.

Theoretical study on the electrocatalytic CO2 reduction mechanisms using carbon-nanotube-supported carbon-based single metal atom catalysts

In this study, five Ni-doped carbon-based single metal atom catalysts supported by carbon nanotubes, which can be used for electrocatalytic CO2 reduction, were constructed. According to their structures, these catalysts include one Ni phthalocyanine (NiPc) molecule, two di- and tri-coordinated Ni-doped carbon nanoribbons, and two di-/tri-coordination Ni-doped graphene, which are denoted as NiPc/CNT, H2(H3)-Ni/CNT, 2(3)-Ni/CNT respectively. We first optimized their structures and studied the adsorption characteristics of CO2 on these catalysts with PBE+D3 method. Additionally, the electronic structure characteristics were then calculated, and the electrocatalytic mechanisms of CO2 reduction to CO, HCOOH, CH3OH and CH4 using these catalysts were studied in detail. It is found that the electrocatalytic activities of these five catalysts for reducing CO2 follow the order of 2-Ni/CNT>3-Ni/CNT>H3-Ni/CNT>H2-Ni/CNT>NiPc/CNT. As can be seen, the di-coordination catalysts perform best, followed by the tri-coordination catalysts, while the four-coordination NiPc-based catalyst performs worst. Moreover, graphene-based materials have stronger catalytic activities than their nanoribbon counterparts. Apart from these facts, these five catalytic materials may exhibit product selectivity at different limiting potentials, and specific reaction products can therefore be synthesized by controlling the potentials. We simultaneously investigated the mechanism of competing hydrogen evolution reactions in the electrocatalytic reduction of CO2 with five catalysts, and in order to inhibit the competing hydrogen evolution reactions and improve the efficiency of CO2 electrocatalytic reduction, the acidity of the solution can be appropriately reduced. We hope that our present work can provide a theoretical foundation for the future design and synthesis of novel carbon-based electrocatalyst for efficient CO2 reduction.

Stepwise on-surface synthesis of nitrogen-doped porous carbon nanoribbons

Precise synthesis of carbon-based nanostructures with well-defined structural and chemical properties is of significance towards organic nanomaterials, but remains challenging. Herein, we report on a synthesis of nitrogen-doped porous carbon nanoribbons through a stepwise on-surface polymerization. Scanning tunneling microscopy revealed that the selectivity in molecular conformation, intermolecular debrominative aryl-aryl coupling and inter-chain dehydrogenative cross-coupling determined the well-defined topology and chemistry of the final products. Density functional theory calculations predict that the ribbons are semiconductors, and the band gap can be tuned by the width of the ribbons.

Flower-like carbon spheres formed by self-assembly of nitrogen-doped porous nanoribbons to boost SnS2 nanosheets for advanced lithium storage

SnS2 is a two-dimensional layered material with high theoretical capacity, but its further application in lithium-ion batteries is limited by problems such as low intrinsic conductivity and dramatic volume expansion during lithiation process. Therefore, SnS2 nanosheets were designed to anchor in the interlayer nanospaces of flower-like carbon spheres self-assembled from nitrogen-doped porous carbon nanoribbons (SnS2/N-FC). Nitrogen-doped porous nanoribbons facilitated the uniform distribution of SnS2 nanosheets in the interlayer nanospaces of the flower-like carbon spheres, establishing a face-to-face interaction with the nanoribbons and the SnS2 nanosheets. This composite structure enhances the transfer of electrons between the components. In addition, the integration of spherical flower-like electrodes with the reserved interlayer nanospaces provided a buffering space for volume expansion which ensured an even distribution of mechanical stress. As a result, SnS2/N-FC exhibited a high reversible specific capacity of 1322.3 mAh g−1 after 200 cycles at 0.1 A g−1, with the capacity kept growing to 1329.4 mAh g−1 after 1000 cycles at 1 A g−1. This study introduces a novel approach for the design of anode materials which demonstrate excellent lithium storage.

Synthesis and functionalization of carbon nanostructures in a single‐step CVD process through the implementation of a recycled precursor

AbstractBackgroundRecycled materials are a major research topics of the new era to relieve pressure on raw material extraction from our planet and reduce its pollution levels. This has helped us to reinvent our relationship with nature, and to commit ourselves to a sustainable economic and social reconstruction. An excellent option to add value to waste while protecting the environment is the synthesis of carbon nanostructures (CNSs) using a recycled material as a precursor. In this research, the synthesis and functionalization of CNSss in a single‐step chemical vapour deposition (CVD) process was carried out using a recycled precursor. The methanol fraction is waste from the distillation process in the production of alcoholic beverages. The synthesis temperatures were 750, 800 and 850 °C.ResultsAs a result, carbon nanotubes, carbon nanoribbons and carbon nanobeads with diameters <100 nm and widths <500 nm were obtained. The crystal size of CNSs decreased with increasing synthesis temperature, from 20 to 12 nm. RAMAN spectra revealed the high degree of graphitization and the presence of different types of nanostructures. Carbonyl (CO) and hydroxide (‐OH) stretching of the carboxylic acid were present in all samples.ConclusionThe results obtained shown that the CNSs synthetized are functionalized in a single‐step CVD process using the methanolic fraction as a precursor. © 2024 Society of Chemical Industry (SCI).

Monitoring SEIRAS on a Graphitic Electrode for Surface-Sensitive Electrochemistry: Real-Time Electrografting.

The ubiquity of graphitic materials in electrochemistry makes it highly desirable to probe their interfacial behavior under electrochemical control. Probing the dynamics of molecules at the electrode/electrolyte interface is possible through spectroelectrochemical approaches involving surface-enhanced infrared absorption spectroscopy (SEIRAS). Usually, this technique can only be done on plasmonic metals such as gold or carbon nanoribbons, but a more convenient substrate for carbon electrochemical studies is needed. Here, we expanded the scope of SEIRAS by introducing a robust hybrid graphene-on-gold substrate, where we monitored electrografting processes occurring at the graphene/electrolyte interface. These electrodes consist of graphene deposited onto a roughened gold-sputtered internal reflection element (IRE) for attenuated total reflectance (ATR) SEIRAS. The capabilities of the graphene-gold IRE were demonstrated by successfully monitoring the electrografting of 4-amino-2,2,6,6-tetramethyl-1-piperidine N-oxyl (4-amino-TEMPO) and 4-nitrobenzene diazonium (4-NBD) in real time. These grafts were characterized using cyclic voltammetry and ATR-SEIRAS, clearly showing the 1520 and 1350 cm-1 NO2 stretches for 4-NBD and the 1240 cm-1 C-C, C-C-H, and N-Ȯ stretch for 4-amino-TEMPO. Successful grafts on graphene did not show the SEIRAS effect, while grafting on gold was not stable for TEMPO and had poorer resolution than on graphene-gold for 4-NBD, highlighting the uniqueness of our approach. The graphene-gold IRE is proficient at resolving the spectral responses of redox transformations, unambiguously demonstrating the real-time detection of surface processes on a graphitic electrode. This work provides ample future directions for real-time spectroelectrochemical investigations of carbon electrodes used for sensing, energy storage, electrocatalysis, and environmental applications.

Si@Fe3O4/AC composite with interconnected carbon nano-ribbons network for high-performance lithium-ion battery anodes

Si-based anode materials have a relatively high theoretical specific capacity and low operating voltage, greatly enhancing the energy density of rechargeable lithium-ion batteries (LIBs). However, their practical application is seriously hindered by the instability of active particles and anode electrodes caused by the huge swelling during cycling. How to maintain the stability of the charge transfer network and interface structure of Si particles is full of challenges. To address this issue, we have developed a novel Si@Fe3O4/AC/CNR anode by in-situ growing one-dimensional high elastic carbon nano-ribbons to wrap Si nanoparticles. This special structure can construct fast channels of electron transport and lithium ion diffusion, and stabilize the surface structure of Si nanoparticles during cycling. With these promising architectural features, the Si@Fe3O4/AC/CNR composite possesses a high specific capacity of 1279.4 mAh/g at 0.5 A/g, and a superior cycling life with 80 % capacity retention after 700 cycles. Even at a high current density of 20.0 A/g, the composite still delivers a capacity of 621.2 mAh/g. The facile synthetic approach and high performance of Si@Fe3O4/AC/CNR anodes provide practical insight into advanced anode materials with large volume expansion for high-energy-density LIBs.

In-based coordination polymer-derived carbon nanoribbons with abundant CoP nanoparticles in carbon nanotubes for water oxidation.

The sluggish oxygen evolution reaction (OER) in overall electrocatalytic water splitting poses a significant challenge in hydrogen production. A series of transition metal phosphides are emerging as promising electrocatalysts, effectively modulating the charge distribution of surrounding atoms for OER. In this study, a highly efficient OER electrocatalyst (CoP-CNR-CNT) was successfully synthesized through the pyrolysis and phosphatization of a Co-doped In-based coordination polymer, specifically InOF-25. This process resulted in evenly dispersed CoP nanoparticles encapsulated in coordination polymer-derived carbon nanoribbons. The synthesized CoP-CNR-CNT demonstrated a competitive OER activity with a smaller overpotential (η10) of 295.7 mV at 10 mA cm-2 and a satisfactory long-term stability compared to the state-of-the-art RuO2 (η10 = 353.7 mV). The high OER activity and stability can be attributed to the high conductivity of the carbon network, the abundance of CoP particles, and the intricate nanostructure of nanoribbons/nanotubes. This work provides valuable insights into the rational design and facile preparation of efficient non-precious metal-based OER electrocatalysts from inorganic-organic coordination polymers, with potential applications in various energy conversion and storage systems.

Carbon nanoribbon formation by in-situ TEM manipulation of a C59N dithiolane derivative encapsulated into SWNTs

Carbon nanoribbon formation by in-situ TEM manipulation of a C59N dithiolane derivative encapsulated into SWNTs

First-principles study on the electronic properties of biphenylene, net-graphene, graphene+, and T-graphene based nanoribbons.

Since the successful separation of graphene, carbon materials with the excellent physical and chemical properties have attracted the interest of a large number of researchers. In this paper, density functional theory combined with non-equilibrium Green's function is used to systematically study the electronic structures of two-dimensional biphenylene, net-graphene, graphene+ and T-graphene, and to reveal the electron transport properties of net-graphene nanodevices under asymmetric regulation. The results show that biphenylene, net-graphene, graphene+, and T-graphene all show metallic properties, in which biphenylene and net-graphene show anisotropy, while graphene+ and T-graphene show isotropy. In addition, for the one-dimensional new carbon based nanoribbons, except for the armchair-edged net-graphene and biphenylene nanoribbons, which exhibit semiconductor properties and a band gap value of 0.08 eV, the rest of the carbon nanoribbons display metal properties. Interestingly, two of them showed a tendency to oscillate and decrease the band gap value with increasing width, while BPN-2 biphenylene nanoribbons directly changed from exhibiting semiconductor to metallic properties with increasing width combination with no oscillation. The electronic transport properties of net-graphene nanoribbons based nanodevice models for electrons transform along zigzag and armchair directions are systematically studied. An obvious negative differential resistance characteristic along the armchair and zigzag directions can be found. Overall, these interesting results show that these new net-graphene nanodevices have good practical application prospects in future electronic nanodevices.

3D grape string-like heterostructures enable high-efficiency sodium ion capture in Ti3C2Tx MXene/fungi-derived carbon nanoribbon hybrids.

2D transition metal carbides and carbonitrides (MXenes) have emerged as promising electrode materials for electrochemistry ion capture but always suffer from severe layer-restacking and irreversible oxidation that restrains their electrochemical performance. Here we design a dual strategy of microstructure tailoring and heterostructure construction to synthesize a unique 3D grape string-like heterostructure consisting of Ti3C2Tx MXene hollow microspheres wrapped by fungi-derived N-doping carbon nanoribbons (denoted as GMNC). The 3D grape string-like heterostructure effectively avoids the aggregation of Ti3C2Tx MXene sheets and enhances the stability of MXenes, providing abundant active sites for ion capture, and an interconnected conductive bionic nanofiber network for high-rate electron transport. In consequence, GMNC achieves a superior adsorption capacity for sodium ions (Na+) in capacitive deionization (CDI) (162.37 mg gNaCl-1) with an ultra-high instantaneous adsorption rate (30.52 mg g-1 min-1) at an applied voltage of 1.6 V and satisfactory cycle stability over 100 cycles, which is a strong performer among the state-of-the-art values for MXene-based CDI electrodes. In addition, in situ electrochemical quartz crystal microbalance with dissipation monitoring (EQCM-D) measurement combined with density functional theory (DFT) reveals the mechanisms of the Na+ capture process in the GMNC heterostructure. This work opens a new avenue for designing high-performance MXenes with a 3D hierarchical heterostructure for advanced electrochemical applications.

Theoretical investigation of width effects in the electronic and transport properties of carbon nanoribbons with 5-8-5 carbon rings: a first-principles study

An increase in width enhances stability and acts like uniaxial tensile strain. Sub-bandgap regions trigger optoelectronic device applications and negative differential resistance. Nanodevice behavior depends on the width.

Carbon nanobelts with zigzag and armchair edge and interlocked carbon nanobelts for chirality

This paper presents a theoretical study on the optical properties of carbon nanobelts with zigzag and armchair edges, as well as interlocked carbon nanobelts for chirality. The results demonstrate that two photon absorption (TPA) and electronic circular dichroism (ECD) techniques can effectively differentiate carbon nanoribbons with different boundaries, revealing their relationship and distinguishing features. The findings from this research contribute to a better comprehension of carbon nanoribbons, mechanically interlocked molecules, and chirality.

Fe phthalocyanine stabilized on phosphorous-doped multi-defective carbon nanoribbons as oxygen reduction electrocatalysts

Coordination polymers can be utilized as ideal precursors due to their ability to change their growth behavior and topological structure through solvent-induced effects. In this work, nanostrip-like crystalline particles, transformed from interchangeable indium-based coordination polymers (InOF-25/26), are treated to synthesize phosphorus-doped multi-defective carbon nanoribbons for efficiently anchoring iron phthalocyanine. The obtained FePc-Fe2P@25-CNR electrocatalyst exhibits a superior half-wave potential of 0.899 V and a large diffusion current density of 5.152 mA cm−2 in oxygen reduction reaction (ORR). Meanwhile, it also shows excellent stability in homemade Zn-air batteries with satisfactory charge/discharge durability over 100 cycles. In this case, the ORR performance can be improved by phosphating the carbon surface, reinforcing tight bonding with transition metal phthalocyanines, and inducing charge migration to increase the electrocatalysis kinetics, which is further validated by relevant theoretical calculation. This synthetic strategy combines structurally variable coordination polymers with metallomacrocyclic molecules, exploiting a feasible pathway for the preparation of high-performance electrochemical catalysts.