Sp2 Carbon Research Articles

Selective oxidation and removal of hydrocarbons from carbon nanotubes using reactive yttrium films

Wrapping polymers are useful for sorting high purity suspensions of semiconducting carbon nanotubes (CNTs) in organic solvents, but for many microelectronic applications the wroapping polymer needs to be removed. Coating wrapped CNTs with yttrium metal, followed by oxidation and removal with dilute aqueous acid, has been used to etch wrapping polymer, but the mechanism, selectivity, extent of etching, and range of conditions over which etching occurs have not been reported. We use spectroscopic and physical measurements to characterize this process on thin films of an archetypical conjugated wrapping polymer (PFO-BPy), its amorphous char residue, CNTs (average diameter 1.5 nm), graphene, and other organic films. Exposure of a yttrium overcoated film of PFO-BPy to ambient air at 20 °C oxidizes a ∼0.5 nm layer of polymer, forming carbonate, carboxylate, and/or carbonyl groups that dissolve in dilute acid. Thicker layers of polymer are removed by repeated cycles. Similar results are observed for other organic films at 20 °C whereas CNTs and graphene are unaltered, providing the selectivity needed to remove carbon-based contaminants from sp2 carbon based nanostructures. Increasing temperature to 250 °C increases polymer oxidation and removal to ∼2.5 nm per cycle; however, the CNTs and graphene are damaged.

Palladium-catalyzed double activation of Si-C(sp3) bond of benzosilacyclobutenes synergized with unexpected olefin migration and ring-opening hydrolysis

A regioselective silicon-carbon bond activation of silacycles has emerged as a powerful strategy to access organosilicon compounds with functional groups. In contrast, progress in the development of new reaction systems for the tandem and double Si-C bond activation of silacycles has lagged. In this regard, there have been no reports of Si-C(sp3) bond activation of benzosilacyclobutenes and its tandem transformations. Herein, we address this challenging, disclosing the first example of palladium-catalyzed double Si-C bond activation of benzosilacyclobutenes and its tandem ring expansion and ring-opening transformations, in which various functionalized silanols that have ester groups are synthesized in this reaction. The main feature of this novel transformation is the highly selective activation of the Si-C(sp3) bond of benzosilacyles to achieve [4 + 2] cycloaddition with ester-activated alkynes and subsequent ring-opening and σ-bond metathesis with H2O. Moreover, the DFT studies realized the origin of Si-C(sp3) bond activation, olefin migration, and ring-opening hydrolysis in the unprecedent reaction process.

New Synthetic Approaches for the Construction of Enantioenriched Molecules Bearing Quaternary Stereocenters

AbstractOptically active molecule architectures stand as an important class of organic compounds and occupy a key role in academic and industrial communities. Particularly, the molecules bearing quaternary carbon are of vital importance because of its favorable conformation and valuable three‐dimensional molecules, which frequently play a key role in a broad spectrum of functional materials, pharmaceutical relevant natural molecules, and agrochemicals. Over the past few decades, a large number of synthetic strategies for the enantioselective construction of compounds with chiral quaternary carbon centers have been the focus of a number of research initiatives. In this review, the state‐of‐the‐art toward the synthesis of enantioenriched molecules bearing quaternary stereocenters are summarized, which could be segmented into four categories: 1) Construction of optically active quaternary carbon centers by addition to prochiral sp2 carbon; 2) Construction of optically active all‐carbon quaternary stereocenters via substitution at non‐chiral tetra‐substituted carbon; 3) Construction of optically active all‐carbon quaternary stereocenters via kinetic resolution; 4) Construction of optically active all‐carbon quaternary stereocenters via desymmetrization reactions.

Cu−based bimetallic sites' p-d orbital hybridization promotes CO asymmetric coupling conversion to C2 products

Hampered by sluggish C−C coupling kinetics, the low selectivity and efficiency have limited industrial applications of CO2 reduction into valuable multi-carbon products. A direct coupling of CO molecules or their coupling after hydrogenation, followed by the final synthesis of C2 products, can help to overcome these limitations potentially. In this study, a detailed high-throughput screening of bimetallic site catalysts comprising copper (Cu) and 28 other metal (M) atoms was conducted. The metal atoms Cu and M were anchored on a carbon nanotube (CNT) with six nitrogen (N6) defects (CuMN6@CNT), which possesses effective dual active sites for C−C coupling. The calculated results demonstrate that the CuGaN6@CNT catalyst exhibited favorable selectivity, with low theoretical overpotentials of −0.23 and −0.34 eV for ethanol and ethylene, respectively, surpassing most reported catalysts. The synergistic effect of Ga and Cu sites, along with their p-d states hybridization, results in an enhancement of Cu's d state dispersion and energy barriers reduction for C−C coupling. Additionally, the strain effect of the substrate CNT exhibits a direct correlation with the catalytic performance of CuGaN6@CNT by adjusting the d-band center of the Cu site and p-band center of the Ga site. These findings provide a novel insights into the electrocatalytic reduction of CO into valuable C2 products using bimetallic single atom catalyst, offering significant guidance for future research endeavors in this field.

Flexomagnetoelectric Effect in Sr_{2}IrO_{4} Thin Films.

Symmetry engineering is explicitly effective to manipulate and even create phases and orderings in strongly correlated materials. Flexural stress is universally practical to break the space-inversion or time-reversal symmetry. Here, by introducing strain gradient in a centrosymmetric antiferromagnet Sr_{2}IrO_{4}, the space-inversion symmetry is broken accompanying a nonequivalent O p-Ir d orbital hybridization along the z axis. Thus, an emergent polar phase and out-of-plane magnetic moment have been simultaneously observed in these asymmetric Sr_{2}IrO_{4} thin films, which both are absent in its ground state. Furthermore, upon the application of a magnetic field, such polarization can be controlled by modifying the occupied d orbitals through spin-orbit interaction, giving rise to a flexomagnetoelectric effect. This Letter provides a general strategy to artificially design multiple symmetries and ferroic orderings in strongly correlated systems.

Cauliflower-like Ni/NiCoP@Boron-doped diamond composite electrodes for high-performance symmetric supercapacitors

Due to the lack of electrocatalytic active sites, the supercapacitors (SCs) even based on the most stable sp3 carbon material (Boron-doped diamond) suffer from poor capacitance and low energy density. Herein, a cauliflower-like biphasic Ni/NiCoP layer has been successfully deposited on the BDD film and further applied as binder-/current collector-free SC electrodes. In a redox-active aqueous electrolyte (0.05 M Fe(CN)63−/4− + 1.0 M KOH), the Ni/NiCoP@BDD electrode with exceptional cyclic stability (∼89.0 % after 10,000 cycles) delivers a specific capacitance of 256.1 mF cm−2 at a current density of 30 mA cm−2, about 2 times higher than that in inert electrolyte. Furthermore, such a symmetric PC device provides a desired energy density of 70.0 Wh kg−1 at a high power density of 3601 W kg−1.

Electronic structure of zaykovite Rh3Se4, prediction, and analysis of physical properties of related materials: Pd3Se4, Ir3Se4, and Pt3Se4.

In this work, we explore the electronic properties and chemical bonding in the recently discovered mineral zaykovite, the first natural rhodium selenide Rh3Se4. We comprehensively studied the bulk electronic structure, hybridization of rhodium and selenium orbitals, and the influence of spin-orbit interaction on the electronic spectrum, as well as inspected its topological properties. In addition, we investigated the surface electronic structure of zaykovite and revealed the anisotropic Rashba-type spin splitting in the surface states. In addition, using calculations of the phonon spectra and enthalpy of formation, we predicted the family of similar selenides based on other 4d and 5d transition metals such as Ir, Pd, and Pt. The structural and electronic properties of these materials are discussed.

One-step synthesis of [15]paracyclophane and [16]paracyclophane via Pd-catalyzed C(sp2)–C(sp3) coupling and the cyclohexane-encapsulating crystal structure of [16]paracyclophane

Abstract Macrocycles consisting of methylene-bridged aromatic rings had been synthesized by aromatic electrophilic substitution reactions, thus limiting the substrates to electron-rich aromatic compounds. In this work, we developed a novel method for 1-step synthesis of [15]paracyclophane (PCP) and [16]PCP by the self-condensation of 4-bromobenzyl bromide via a Pd-catalyzed desulfinative coupling reaction between C(sp2) and C(sp3) carbon atoms. In the crystal structure, [16]PCP encapsulated cyclohexane and formed a 1D columnar structure

Conversion of Nitrate to Ammonia by Amidinothiourea-Coordinated Metal Molecular Electrocatalysts with d-π Conjugation.

The electrochemical reduction of nitrate to ammonia (NO3RR) provides a desired alternative of the traditional Haber-Bosch route for ammonia production, igniting a research boom in the development of electrocatalysts with high activity. Among them, molecular electrocatalysts hold considerable promise for the NO3RR, suppressing the competing hydrogen evolution reaction. However, the complicated synthesis procedure, usage of environmentally unfriendly organic solvents, and poor stability of Cu-based molecular electrocatalysts greatly limit their employment in NO3RR, and the development of desired Cu-based molecular catalysts remains challenging. Herein, a simple nonorganic solvent involving a one-step strategy was proposed to synthesize d-π-conjugated molecular electrocatalysts metal-amidinothiourea (M-ATU). Cu-ATU is composed of Cu coordinated with two S and two N atoms, whereas Ni-ATU is formed by Ni with four N atoms from two ATU ligands. Remarkably, Cu-ATU with a Cu-N2S2 coordination configuration exhibits superior NO3RR activity with a NH3 yield rate of 159.8 mg h-1 mgcat-1 (-1.54 V) and Faradaic efficiency of 91.7% (-1.34 V), outperforming previously reported molecular catalysts. Compared to Ni-ATU, Cu-ATU transfers more electrons to the *NO intermediate, effectively breaking the strong sp2 hybridization system and weakening the energy of N═O bonds. The increase in free energy of *NO reduced the energy barriers of the rate-determining step, facilitating the further hydrogenation process over Cu-ATU. Our work opened up a new horizon for exploring molecular electrocatalysts for nitrate activation and paved a way for the in-depth understanding of catalytic behaviors, aligning more closely with industrial demands.

Synergistic Pd(OAc)2/CuI-catalyzed alkynylation of β-lactam derivative via Sonogashira coupling

Herein, a novel approach of bimetallic Pd(OAc)2/CuI-catalyzed alkynylation of 3-chloroazetidin-2-one (β-lactam derivative) with terminal alkyne via tandem C–C bond activation/Sonogashira-type cross-coupling reaction is developed. This synthesis encompasses a sequence of inert Csp3–X/Csp–H functionalization processes involving the coupling of the C(sp3) adjacent to the 3-chloroazetidin-2-one with the C(sp) of a terminal alkyne. The final analogs are synthesized by means of the indole-benzothiazole Schiff base formation, cyclization of the Schiff base to generate the β-lactam derivative, and Sonogashira coupling to afford a C(sp3)–C(sp) bond. In addition, indole, benzothiazole, and azetidine-2-one have been identified to be highly efficient heterocyclic scaffolds with a range of pharmacological benefits. It encouraged us to discover a hybrid compound that had each of these moieties. Cooperation between two different metals is essential for the successful implementation of this approach. Specifically, the interaction between the Pd and Cu centers in the transmetallation step is depicted through a plausible mechanistic route. The reaction conditions have been optimized by varying catalyst and ligand loadings, bases, temperatures, and solvents. The reaction is highly efficient, yielding alkynylated products in up to 84 % yield with a wide range of substrates and functional group tolerance, thereby serving as a functional model for the Sonogashira coupling reaction.

A DFT study of the second-order nonlinear optical properties of [22]smaragdyrin-BF2-NiII porphyrin fused hybrids

Nonlinear optical response of four [22]smaragdyrin-BF2 (S)-NiII porphyrin (P) fused hybrids were explored by using DFT at CAM-B3LYP/6–31 + G(d)/SDD level of theory. We choose two types of hybrids, SP and PSP fused hybrids, for our study. Calculations indicate that these fused hybrids might be promising candidates for NLO materials based on considerable static and dynamic hyper-Rayleigh scattering (HRS) hyperpolarizability. The PSP fused hybrids possess larger first hyperpolarizabilities values compared to SP hybrids. Further analysis of hyperpolarizability density reveals the nature of the large first hyperpolarizability of the PSP fused hybrids. For all compounds, HRS hyperpolarizability at λ = 1907 nm is higher than the static value. After the interpretation of dipolar and octupolar character of βHRS, these hybrids show the high dipolar character.

Size and chemistry of 1–2 layer graphene nanosheets at the transition into photoluminescence and assembly with large shifts from blue to red emission

Synthetic refinement of graphene photoluminescence remains challenging because underlying characteristics have not been well understood from polydisperse mixtures of different sizes and surface chemistries. Here, we isolate and characterise different populations of 1–2 layer graphene (1-2LG) each with narrow size range. Small 1-2LG nanosheets down to 25 nm size remained black and non-luminescent with N. and O. additions at their edges, whereas 15 nm nanosheets transitioned into photoluminescence, while retaining substantial sp2 carbon of graphene. Positively-charged amine modifications overcame the repulsion between nanosheets from the negative zeta potential of sp2 graphene faces in water and allowed assembly of similarly-sized nanosheets with large red shifts (>150 nm) taking blue emission into the red. However, more extensive edge modification into carboxyl groups and neutral amides built negative charge at the edges. Together with smaller nanosheet size and reduced sp2 carbon, red shifts were weakened by half in these isolates, which were most modified and more like graphene oxide and carbon quantum dots. N addition to form amines at nanosheet edges, while avoiding O atom addition and carboxyl groups, presents as a simple refinement for synthesis of self-assembling graphene quantum dots with multi-colour emission, which also retain sp2 carbon properties of graphene.

Investigation of thermal transport mechanism of silicone-modified phenolic matrix nanocomposites with different pyrolysis degrees

Polymeric nanocomposites with low thermal conductivity show promising applications for next-generation thermal protection materials used in re-entry vehicles due to their lightweight, high char yield, and excellent ablation-oxidation resistance. However, the thermal conductivity of polymeric nanocomposites varies with the pyrolysis degree of the polymer matrix in aerodynamic environments, which significantly affects thermal protection and structural applications but is challenging to identify experimentally. Herein, non-equilibrium molecular dynamics simulations combined with experiments were implemented to determine the dependence of thermal conductivities on pyrolysis degree and microstructures for polymeric nanocomposites. We further explore the thermal transport mechanism through various contributions to the morphology. The results show that the thermal conductivity of the polymer matrix can be increased by a factor of 4.44 (from 0.27 W/m/K to 1.47 W/m/K) as the pyrolysis degree increases from 0 to 100%, and the thermal conductivity depends nonlinearly on the pyrolysis degree and temperature. Molecular dynamics simulations found that the side chains of the polymer matrix are rapidly scissored with the increasing pyrolysis degrees, and the structural ordering of the residual solids containing sp2 hybridization is enhanced, exhibiting graphene-like microtopological features, which reduces phonon scattering and makes thermal transport more efficient. This work provides insight into the linkage between the thermal transport properties and the pyrolysis degree of polymeric nanocomposites, which is valuable for improving the thermal transport performance and modeling ablation response for polymeric nanocomposites.

Hybrid CoFe2O4-CNTs-graphene: Synthesis and characterization for energy storage devices

Hybrid materials play a crucial role in a spectrum of energy storage devices. Among them CoFe2O4–CNT–graphene hybrid stands out as versatile magnetic materials with wide-ranging applications spanning electronics, magnetism, and sensor industries. In this study, we synthesized CoFe2O4–CNT–graphene hybrid utilizing ultrasonication method. This fabrication method resulted in the formation of CoFe2O4 nanoparticles, along with bamboo-like carbon nanotubes (CNTs) and graphene nanosheets which collectively establish an open three-dimensional structure. Thorough analyses were conducted on the synthesized nano-composites employing various characterization techniques such as XRD, FT-IR, Raman and FESEM. Further characterization through XPS confirmed the formation of spinel ferrites, detecting the presence of carbon sp2, C1s, carboxylates (O-C-OH), and sp3 carbon, indicating the presence of carbon‑carbon (CC) bonds and confirms the energy levels of Co2p1/2 and Co2p3/2 indicating the effective incorporation of CFO onto the CNT/graphene surface. Analysis of dielectric parameters revealed promising characteristics for high-frequency devices, attributed to low dielectric loss, high quality factor, short relaxation time, and diverse responses exhibited by these materials. The M–H loops of the composite samples displayed ferromagnetic hysteresis behavior due to the presence of ferrite in the matrices. The coercivity value shows a slight improvement in the hybrid samples, while saturation magnetization values decrease, indicating a 1:1 weight ratio of ferrite particles to the host matrix with the incorporation of nonmagnetic CNTs and graphene, and the Hc value increases with the addition of these carbon-based materials due to increased surface anisotropy energy. Upon evaluation of dielectric and magnetic properties the hybrid materials demonstrated an enhanced dielectric and magnetic properties which render these materials suitable for utilization across a spectrum of energy storage devices.

Investigating Layered Topological Magnetic Materials as Efficient Electrocatalysts for the Hydrogen Evolution Reaction under High Current Densities

Despite considerable progress, high-performing durable catalysts operating under large current densities (i.e., >1000 mA/cm2) are still lacking. To discover platinum group metal-free (PGM-free) electrocatalysts for sustainable energy, our research involves investigating layered topological magnetic materials (semiconducting ferromagnets) as highly efficient electrocatalysts for the hydrogen evolution reaction under high current densities and establishes the novel relations between structure and electrochemical property mechanisms. The materials of interest include transition metal trihalides, i.e., CrCl3, VCl3, and VI3, wherein a structural unit, the layered structure, is formed by Cr (or V) atoms sandwiched between two halides (Cl or I), forming a tri-layer. A few layers of quantum crystals were exfoliated (~50−60 nm), encapsulated with graphene, and electrocatalytic HER tests were conducted in acid (0.5M H2SO4) and alkaline (1M KOH) electrolytes. We find a reasonable HER activity evolved requiring overpotentials in a range of 30–50 mV under 10 mA cm−2 and 400−510 mV (0.5M H2SO4) and 280−500 mV (1M KOH) under −1000 mA cm−2. Likewise, the Tafel slopes range from 27 to 36 mV dec−1 (Volmer–Tafel) and 110 to 190 mV dec−1 (Volmer–Herovsky), implying that these mechanisms work at low and high current densities, respectively. Weak interlayer coupling, spontaneous surface oxidation, the presence of a semi-oxide subsurface (e.g., O–CrCl3), intrinsic Cl (or I) vacancy defects giving rise to in-gap states, electron redistribution (orbital hybridization) affecting the covalency, and sufficiently conductive support interaction lowering the charge transfer resistance endow the optimized adsorption/desorption strength of H* on active sites and favorable electrocatalytic properties. Such behavior is expedited for bi-/tri-layers while exemplifying the critical role of quantum nature electrocatalysts with defect sites for industrial-relevant conditions.

Electrocatalytic properties of transition metal vanadates (T = Ti, Cr, Mn, & Fe) for overall water splitting

In this work, first row transition metal vanadates (TMVs), including titanium vanadate (TiV), chromium vanadate (CrV), manganese vanadate (MnV), and iron vanadate (FeV), were synthesized and investigated their electrocatalytic performance for the alkaline water splitting. The prepared TMVs showed easy electron transfer characteristics and tunable band structures, and among these TMVs, the synthesized FeV demonstrated the best electrocatalytic bifunctional activities for both HER (η100 = 375 mV) and OER (η100 = 260 mV) with a significant electronic and morphological stability over 100 h operation. The examination of electronic structure revealed that the balanced catalyst-intermediate interaction through optimum d-p orbital hybridization in FeV, adhering to the Sabater principle, vouched for such facile redox reaction. The structural stability might be attributed to the synergism between iron and vanadate as the multivalent Fe adjusted the shift in vanadium coordination when the oxidation state of Vn+ (n = 3–5) changed. Moreover, the two-electrode system of FeV || FeV in a single electrolyzer demonstrated superior cell voltage100 of 1.86 V in comparison to commercial Pt/C || IrO2 electrodes (1.91 V). This work offers facile perspective to produce TMVs as the efficient electrocatalysts for green synthesis of fuel gases.

Chemo- and diastereoselective four-component reactions with Rh carbynoids

Multi-component reactions (MCRs) provide an efficient method for constructing multiple chemical bonds by combining three or more starting materials in a single operational step, enabling rapid and cost-effective synthesis of structurally diverse compounds. Although carbynoids (R-C:+) have shown potential for the development of selective MCRs due to their unique carbene and carbocation characteristics, their application in four-component reactions (4CRs) has been constrained by challenges in chemoselectivity. Herein, we provide a general solution to the challenges of chemoselective 4CR, using halo diazo reagents as carbynoid precursors, followed by reacting with pyrazoles, alcohols and imines sequentially. This approach allows the simultaneous construction of three different C(sp3)-N, C(sp3)-O, and C(sp3)-C(sp3) bonds on the same carbon. The success of this protocol mainly depends on precise control of chemical kinetics. Detailed experimental studies elucidate that the generation rate of aza-Rh(II)-carbene is faster than oxy-Rh(II)-carbene.

Enhanced electrochemical performance of flexible carbon substrates via carbonized layer of oxidant-induced polydopamine for high-performance supercapacitors

Flexible substrates are essential for advancing energy storage materials in portable and wearable devices. Carbon cloth is a promising option due to its flexibility and lightweight properties, but its high electrical resistance and hydrophobic surface present challenges for solution-based electrolytes. To overcome these issues, a surface modification technique was developed that coats carbon cloth with dopamine and subsequently carbonizes it. This process enhances hydrophilicity while preserving the sp2 carbon structure, significantly improving electrical conductivity. The chemical bath deposition of Ni(OH)2 onto the carbonized polydopamine-coated carbon cloth produced a uniform layer that increased specific capacitance dramatically. At a current density of 1 A/g, the specific capacitance reached 1100F/g, compared to 919F/g for Ni(OH)2 on unmodified carbon cloth. Furthermore, the electrodes maintained high specific capacitance at higher current densities, showcasing superior rate capability. Overall, carbonized polydopamine layers effectively reduce electrical resistivity and hydrophobicity, enhancing the performance of carbon-based materials for energy storage applications.

Simulated hydrogen diffusion in diamond grain boundaries

To evaluate hydrogen diffusion within diamond, a series of molecular dynamics simulations have been carried out in which diffusion coefficients and activation energies were determined. Diamond grown via chemical vapour deposition (CVD) contains a high hydrogen concentration within grain boundaries, because of this, common tilt grain boundaries were recreated from transmission electron microscopy images taken from literature. Diffusion coefficients of hydrogen placed within the grain boundary were estimated and compared to the bulk diffusion. Unlike many crystalline structures, some grain boundaries presented limited diffusion when compared to the bulk. Diffusion characteristics of grain boundaries are thought to be a result of channelling effects combined with the formation of sp3C-H bonds with sp2 carbon present within some grain boundaries - increasing and decreasing diffusion rates respectively. Potential wells were observed across some but not all the grain boundaries resulting in hydrogen trapping and anisotropic diffusion.

A Porphyrin-Based sp2 Carbon-Conjugated covalent organic polymer containing flexible chains for efficient heterogeneous photocatalysis

Porphyrin based covalent organic polymers are excellent catalysts. Herein, a sp2 carbon linked porphyrin based organic polymer H2Pp-PDAN was designed and synthesized by co-condensation of porphyrin monomer containing flexible chains H2Pp with 1, 4-phenylenediacetonitrile PDAN. As photocatalysts, H2Pp-PDAN exhibited excellent photocatalytic performance for photocatalytic oxidative coupling of amines, and was successfully used for 15 consecutive reactions with no detectable reduction of the catalytic activity. H2Pp-PDAN showed good photocatalytic activity and excellent recyclability for photocatalytic oxidation of thioanisole to methyl phenyl sulfoxide. Mechanistic studies revealed that the photocatalytic oxidation of benzylamine coupling by H2Pp-PDAN proceeds via both energy transfer and electron transfer pathways.