Graphdiyne Nanosheet Research Articles

Computational investigation of charge injection into modified graphdiyne nanosheet via Al doping and Li decoration to improve hydrogen adsorption

The utilization of hydrogen as a clean fuel has been made feasible by the expanding development of cutting-edge materials for hydrogen adsorption and storage. In this study, we thoroughly assessed hydrogen storage capability on both neutral and charge-injected graphdiyne (GDY) nanosheets modified with Al doping and Li decorating (Li.Al-GDY). According to the findings, pure GDY has an adsorption energy of −0.093 eV, while GDY modified with Al and Li atoms has an improved adsorption energy of −0.577 eV. The highest H2 adsorption energy of −0.760 eV was calculated for the applied charge of −2 e to the Li.Al-GDY nanosheet, indicating a significant enhancement in the adsorption energy with the charge injection. While the pristine GDY nanosheet serves as a very poor H2 molecule adsorber and cannot even hold one H2 molecule, the charged Li.Al-GDY nanosheet maintains 13 H2 molecules with an average adsorption energy of −0.287 eV. According to the results, injecting charge into the nanosheet along with modification techniques such as doping and decorating can significantly boost the effectiveness of weak carbon adsorbents in terms of hydrogen adsorption. Such approaches enable the realization of the goal of using carbon adsorbents as H2 green fuel storage.

Template Based Synthesis of Porous Graphdiyne Nanosheet for Reversible and Fast NO2 Detection by UV Irradiation.

Two-dimensional graphdiyne (GDY) formed by sp and sp2 hybridized carbon has been found to be an efficient toxic gas sensing material by density functional theory (DFT). However, little experimental research concerning its gas sensing capability has been reported owing to the complex preparation process and harsh experimental conditions. Herein, porous GDY nanosheets are successfully synthesized through a facile solvothermal synthesis technique by using CuO microspheres (MSs) as both template and source of catalyst. The porous GDY nanosheets exhibit a broadband optical absorption, rendering it suitable for the light-driven optoelectronic gas sensing applications. The GDY-based gas sensor was demonstrated to have excellent reversible to NO2 behaviors at 25 °C for the first time. More importantly, higher response value and faster response-recovery time once exposed to NO2 gas molecules are achieved by the illumination of UV light. In this way, our work paves the way for the exploration of GDY-based gas detection experimentally.

Molecular modeling for sensing of cisplatin drug by graphdiyne: electronic study via DFT.

By utilizing first-principles calculations, we studied the electronic properties of graphdiyne nanosheet (GDY) and its Si-doped counterpart, Si-GDY. Both GDY and Si-GDY sheet surfaces were examined for the drug cisplatin (CP) adsorption using adsorption energy, charge transfer, and changes in electrical conductivity as indicators. Pure GDY has little affinity for CP, according to this study. Only 7.83% of the GDY surface's bandwidth energy changed after CP adsorption. CP on Si-GDY has a gaseous energy value of -18.75kcal/mol and an aqueous energy value of - 49.39kcal/mol. The prescribed medications' water-phase solubility is determined by their solvation energy value. These charges are transferred between CP and the Si-GDY sheet, which is extremely positively charged, and this gives CP the necessary binding energy. After CP adsorption, electrical conductivity of Si-GDY increased by approximately 19.01%.

Understanding the performance of graphdiyne membrane for the separation of nitrate ions from aqueous solution at the atomistic scale

A molecular dynamics simulation study is conducted to investigate the capability of the pristine graphdiyne nanosheet for nitrate ion separation from water. The removal of nitrate ion contaminants from water is of critical importance as it represents an environmental hazard. The graphdiyne is a carbon-based membrane with pore density of 2.4 × 1018 pores/m2 and incircle radius of 2.8 Å. We show that the efficient water flow is accurately controlled through fine regulation of the exerted hydrostatic pressure. The high water permeability of 6.19 L.Day−1cm−2MPa−1 with 100% nitrate ions rejection suggests that the graphdiyne can perform as a suitable membrane for nitrate separation. The potential of mean force analysis of the single water molecule and nitrate ion indicated the free energy barriers for nitrate of about 4 times higher than that of water molecules. The results reveal the weak interaction of the water molecules and the membrane which aid to high water flux.

Sensing of Acetaminophen Drug Using Silicon-Doped Graphdiyne: a DFT Inspection.

Using first-principles calculations, we studied the electronic properties of graphdiyne (GDY) nanosheet and its Si-doped counterpart, SiGDY. Both GDY and SiGDY sheet surfaces were examined for acetaminophen (AP) drug adsorption using adsorption energy, charge transfer, and change in electrical conductivity (as indicators). As shown in this study, pure GDY has little affinity for AP. In specific, only 7.83 percent of the GDY surface's bandwidth energy changed after AP adsorption. On SiGDY, AP has a gaseous energy value of - 18.75kcal/mol, as well as an aqueous energy value of - 49.39kcal/mol. The water-phase solubility of the prescribed medications is determined using their solvation energy value. These charges are transferred between AP and the SiGDY sheet, which is extremely positively charged, giving AP the necessary binding energy. After AP adsorption, the electrical conductivity of SiGDY was increased by approximately 19.01 percent.

The effect of the electric field intensity on the hydrogen storage of B/N-co-doped graphdiyne nanosheet

The importance of substituting fossil fuels with clean and renewable energies, and the introduction of hydrogen as a promising option in this field is one of the most popular challenges for researchers. Here, we performed the spin-polarized DFT calculations to investigate the ability of the hydrogen adsorption and storage of modified graphdiyne (GDY) by B and N atoms (BN-GDY) under positive and negative external electric fields. Our findings show that the BN-GDY nanosheet has a weak interaction with the H2 molecule in absence of the electric field, and the electric field can effectively improve this interaction and increase the adsorption energy of the H2 molecule on the BN-GDY nanosheet. Also, the negative electric field has more effect relative to the positive one, and with increasing the intensity of the electric field, the adsorption energy has an upward trend. At the highest intensities of positive and negative applied fields (±0.046 V/Å), the BN-GDY nanosheet can store up to 4 and 8H2 molecules with the average adsorption energies of −0.253 and −0.258 eV/H2, and the H2 storage capacity can reach up to 3.59 and 6.93 wt%, respectively. The preference of our work for practical application is the free metal promotion of H2 adsorption and storage.

Quantum chemical study the interaction between thiotepa drug and silicon doped graphdiyne

By using the calculation of the first principles, we examined the electronic features of pristine graphdiyne nanosheet (GDY) and Si-doped graphdiyne (SiGDY). Moreover, the adsorption of thiotepa (TPA) drug at both GDY and SiGDY sheet surfaces by energy of adsorption, charge transfer (CT), and change electrical conductivity have been investigated. It is proved, the inclination of pristine GDY to TPA drug is insignificant. In addition, the bandwidth energy has changed only about 7.85%, after adsorbing TPA on the GDY surface. Whereas, in the gaseous and aqueous phase, the energy value of TPA adsorption on the SiGDY has been determined about −18.75 and −49.39 kcal/mol, respectively. The solvation energy value exhibits the solubility of the recommended medicines in water phase. Also, the prerequisite for adsorption of the TPA with appropriate binding energies is a noticeable charge transfer between the TPA and SiGDY sheet, which delivers silicon with a considerable positive charge. Further, SiGDY is an electronic sensor for TPA detection unlike pristine GDY, because the electrical conductivity of SiGDY has been increased by about 20.62% after TPA adsorption.

Graphdiyne/CdSe quantum dot heterostructure for efficient photoelectrochemical water oxidation

The design and synthesis of efficient catalysts for water oxidation is of significant importance. Here a type of graphdiyne (GDY) based heterostructure of CdSe/GDY was synthesized through a facile in-situ growth strategy including the first growth of GDY nanosheet arrays followed by the nucleation and growth of CdSe quantum dots (QDs) featuring well-dispersed CdSe QDs with uniform size around 3 nm. Experimental results revealed that GDY could effectively induce the growth and well-dispersion of CdSe QDs on GDY, forming new heterostructures and leading to the maximized number of active sites, the reduced recombination of photo-induced electron and hole pairs, and facilitated charge transfer behavior. Benefiting from these superior advantages, CdSe/GDY achieves greatly enhanced catalytic activity toward water oxidation under light illumination, with a small overpotential of 155 mV at the current density of 10 mA cm−2, which is better than those of pristine CdSe QDs and GDY.

Graphdiyne nanosheet as a novel sensing platform for self-enhanced electrochemiluminescence of MOF enriched ruthenium (II) in the presence of dual co-reactants for detection of tumor marker

Graphdiyne (GDY) is a new two-dimensional carbon material with high charge carrier mobility, excellent conductivity, more suitable band gap, and natural pores was introduced as a new electrochemiluminescent sensing platform. Herein, the metal organic framework (MOFs) used for enrichment of luminophore with grafting Ru(bpy)2(phen-NH2)2+(Ru-complex) and Ru-complex amine-rich nitrogen-doped carbon nanodots(Ru-NCNDs) via both encapsulating and external decoration and decoration of SmS2 QDs as coreactant. Then, the MOF enriched Ru-complex (Ru@MOF@NCNDs-Ru@SmS2 QD) located on a GDY modified ITO electrode developed as a novel and efficient ECL platform. According to the Density Functional Theory (DFT) calculation, the band gap of graphdiyne/Ru(bpy)2(phen-NH2)2+ system decreased compared to graphdiyne, Ru-complex and also graphene oxide/Ru(bpy)2(phen-NH2)2+system, which enhanced (2 folds) the signal response of the presented ECL platform. The ECL response signal of the suggested emitter with high ECL efficiency (13.34%) increased 8 and 4 folds compared to GDY/Ru-NCNDs and GDY/Ru@MOF@NCNDs-Ru as platforms, respectively. The proposed ECL platform applied for CA19-9 antigens detection at concentration range 0.0005 UmL−1 to 200 UmL−1 and detection limit of 0.00013 UmL−1.The development of GDY based platform for decorating nano luminophores, not only provides the design of ECL luminophores with high performance but also promises the application of the presented strategy for fabrication of ultrasensitive bio affinity sensors as candidates in clinical monitoring and diseases diagnostics.

Investigation of the adsorption behavior of two anticancer drugs on the pristine and BN-doped graphdiyne nanosheet: A DFT-D3 perception

Hydroxyurea (HU) and 5-Fluorouracil (FU) are well-known drugs that are widely used in the treatment of cancers. Interaction of the HU and FU molecules on the pristine graphdiyne (GDY) and BN-doped graphdiyne (BNGDY) nanosheet was evaluated by density functional theory (DFT) method in gas and solution phases. Various adsorption sites of GDY/BNGDY have been examined for different HU/FU drug orientations. The results indicate that the 18-membered ring area and top of the acetylenic linkage are the most suitable sites, unlike the hexagonal ring. The S1, S6, S8, and S10 structures are the most stable configurations for GDY/HU, GDY/FU, BNGDY/HU, and BNGDY/FU with the highest Eads about −0.598, −0.417, −1.289, and −0.603 eV in the gas phase and −0.960, −0.592, −1.599 and −1.485 eV in solution phase, respectively. For GDY + HU/FU, the highest Eads is due to interaction of hydrogen atom of drug with GDY; while, in BNGDY+HU/FU, the oxygen atom of drug interacts effectively with the boron atom of the sheet. Likewise, in GDY complexes, charge transfer occurs from sheet to drug, but it is inverse in BNGDY complexes. The band gap values of the GDY and BNGDY are 0.470 and 0.486 eV, respectively, that drug adsorption decreases them in the range of 2.34 to 22.43%. Adsorption behavior of the structures is further discussed and interpreted using quantum molecular descriptors, band structure, and PDOS diagrams. Recovery time values show that in the field of targeted drug delivery and nanomedicine, GDY and BNGDY are more suitable as carrier for the HU and FU drugs, respectively.

Study the Adsorption of Letrozole Drug on the Silicon Doped Graphdiyne Monolayer: a DFT Investigation

In the current study, by employing first-principles computations, the adsorption behavior of letrozole (LET) was investigated on the pristine graphdiyne nanosheet (GDY) as well as Si-doped graphdiyne (SiGDY). According to the adsorption energy, charge transfer value, and the change in the bang gap energy, the tendency of the pristine GDY towards LET is insignificant. However, the interaction of LET with SiGDY was strong and the adsorption energy was approximately − 19.20 kcal/mol. In addition, the associated electrical conductivity with SiGDY increased by approximately 23.53 % following the adsorption of LET. The results show that SiGDY can be employed as an electronic sensor to detect LET. Furthermore, LET is detected by SiGDY in the water phase based on the magnitude of solvation energy. Finally, a considerable charge-transfer between LET and SiGDY is a precondition for the adsorption of the LET molecule with proper binding energies, which delivers the Si atoms with a significant positive charge.

Study the adsorption process of 5-Fluorouracil drug on the pristine and doped graphdiyne nanosheet.

The electronic properties of pristine graphdiyne nanosheet (GDY) and boron-doped graphdiyne (BGDY) were scrutinized using the first-principles calculation. Furthermore, the adsorption energy, charge transfer, and electrical conductivity variation of the 5-fluorouracil (5FU) drugs on both the GDY and BGDY sheet surfaces were reported and were employed to investigate the binding among them. The tendency of pristine GDY to 5FU drug was already identified to be negligible. Moreover, the band gap energy was changed only around 3.31% after 5FU adsorption on the GDY sheet. The adsorption energy of 5FU on the BGDY was computed in both gas and water solvent media and was about - 32.72 and - 41.96kcal/mol, respectively. The moderate amount of solvation energy indicates the good solubility of the implemented drugs in the aqueous medium. Moreover, significant transfer of charge from the 5FU to the BGDY sheet results in a substantially positive charge for B, which is a prerequisite of the adsorption of the 5FU molecule with the suitable binding energy. In addition, after 5FU adsorption, the electrical conductivity of BGDY was increased by about 25.5%, and based on this result, the BGDY is a suitable electronic sensor for 5FU detection unlike to pristine GDY.

Graphdiyne-supported palladium-iron nanosheets: A dual-functional peroxidase mimetic nanozyme for glutathione detection and antibacterial application

Multifunctional enzymatic nanomaterials (nanozymes) with good biocompatibility, strong enzymatic activity, and substrate specificity are the desired alternatives to natural enzymes. Here, the design of a peroxidase mimetic nanozyme capable of detecting and depleting glutathione (GSH) in the bacterial cells is presented. The nanozyme palladium-iron nanostructure decorated graphdiyne nanosheet (PdFe/GDY) was prepared by a facile hydrothermal approach. It can efficiently catalyze the decomposition of H2O2 to produce •OH by a peroxidase-like mechanism. Surprisingly, the PdFe/GDY nanozymes can detect GSH in bacteria with excellent specificity and ultra-low detection limit of 24.45 nM. Moreover, the PdFe/GDY nanozymes can consume GSH for bacterial disinfection with killing efficacy > 99.99%, promote wound healing and do not cause significant toxicity in vitro and in vivo. To our knowledge, this is the first example of a GDY-based nanozyme biosensor and antibacterial agent. Collectively, this work would be indicative to construct GDY-based nanozymes in clinical diagnosis and sterilization.

Detection of odor quality and ripening stage of Mangifera indica L. by graphdiyne nanosheet - a DFT outlook

Using first-principles calculation, geometrical stability together with electronic properties of graphdiyne nanosheet (Gdn-NS) is investigated. The structural stability of Gdn-NS is established with the support of phonon band structure and cohesive energy. The main objective of the present study is to check the odor quality of Mangifera indica L. (mangoes) fruits during the various ripening stage with the influence of Gdn-NS material. In addition, the adsorption of various volatiles, namely ethyl butanoate, myrcene, (E,Z,Z)-1,3,4,8-undecatetraene and $\gamma$-octalactone aromas on Gdn-NS is explored with the significant parameters including Bader charge transfer, energy gap, average energy gap changes and adsorption energy. The sensitivity of volatiles emitting from various ripening stages of mango on Gdn-NS were explored with the influence of density of states spectrum. The outcomes of the proposed work help us to check the ripening stage and odor quality of Mangifera indica L. by Gdn-NS material using density functional theory.

Molecular insights into water desalination performance of pristine graphdiyne nanosheet membrane

Desalination is an exciting technology to solve the global water problem. In recent years, the graphyne-based membranes have been paid much attention to water purification, because of their high resistance and efficiency, as well as low production cost. Herein, the molecular simulations were done to investigate the salt rejection from aqueous solution through the pristine graphdiyne (graphyne-2) nanosheet. For this purpose, a simulation cell including an aqueous solution of sodium and chloride ions and a graphdiyne membrane has been considered. For ion rejection from aqueous solution, a range of hydrostatic pressures was applied to the box. The water density, radial distribution function, and water density map analysis were studied to investigate the structure of water molecules in different parts of the simulation box including the feed side and the pure water side. The results demonstrated that the graphdiyne membrane has 100% salt rejection at pressures <400 MPa, and its permeability is higher than conventional polymeric membranes.

Nonlinear optical response of sodium based superalkalis decorated graphdiyne surface: A DFT study

In the current study, structural, electronic, optical and nonlinear optical properties of superalkalis doped graphdiyne (GDY) complexes (Na2Y@GDY, Y = SH, OCH3, SCH3, CN and N3) are investigated. Our results show that superalkalis cluster preferably adsorb on the hollow cavity of GDY nanosheet. Na2CN@GDY is thermodynamically stable among all considered complexes. NBO analysis reveals the transfer of charge from superalkalis to GDY is analyzed through. Doping of superalkalis on GDY significantly reduces the HOMO-LUMO gap of GDY. Na2OCH3@GDY complex has the lowest H-L gap (3.77 eV) with remarkable βo (6.17 × 104 au) value. The doping of GDY with superalkali introduces excess electrons into the system which significantly reduces the HOMO-LUMO gap by generating new HOMO orbitals. The involvement of superalkalis in diffusion of excess electrons towards GDY is confirmed through PDOS spectral analysis. Furthermore, the two-level model and first hyperpolarizability (βvec) justified NLO properties of superalkalis doped GDY. According to the two-level model, the ΔE is the key factor for the enhancement of first hyperpolarizability values of all newly designed complexes.

Graphdiyne nanosheets as a sensing medium for formaldehyde and formic acid – A first-principles outlook

Formaldehyde and formic acid (in its vapor form) are considered as target vapors in the current study, and the ability of graphdiyne nanosheet to detect target vapors is scrutinized. First and foremost, the stable conduct of the intended prime material, graphdiyne nanosheet is ascertained with the help of cohesive formation energy. Furthermore, the electronic characteristics like band structure, the projected density of states spectrum and electron density are investigated for the solitary and target vapor adsorbed graphdiyne nanosheet. Finally, the adsorption characteristics of the target vapor on the chief component namely the Bader charge transfer, adsorption energy and average energy gap variation are assessed for all the cases. The investigation, as a whole, suggests the deployment of graphdiyne nanosheet as a chief component in detecting formaldehyde and formic acid vapors.

Graphdiyne-Based One-Step DNA Fluorescent Sensing Platform for the Detection of Mycobacterium tuberculosis and Its Drug-Resistant Genes.

The accurate and early detection of Mycobacterium tuberculosis (Mtb) is of great significance for the clinical diagnosis and treatment of tuberculosis. In this work, we report a facile method for the controllable synthesis of a novel few-layered two-dimensional graphdiyne nanosheet (GDY NS) with a thickness of only ∼0.9 nm via an electrochemical lithium-intercalation strategy, which possesses a prominent fluorescence quenching effect. The few-layered GDY NS with its strong adsorptivity for single-stranded DNA is first proposed as a new fluorescent sensing platform for the real-time detection of DNA with excellent specificity, multiplicity, and superhigh sensitivity (limit of detection as low as 25 pM). This sensing platform can be further applied for the Mtb detection from clinical samples and the identification of drug-resistant mutants with a low background and a high signal-to-noise ratio. Herein, we provide a potential basis for the clinical development of rapid, sensitive, and accurate substitutes for the molecular diagnosis of Mtb and its drug-resistant genes.

Investigation on graphdiyne nanosheet in adsorption of sorafenib and regorafenib drugs: A DFT approach

We investigated the electronic characteristics of graphdiyne nanosheet (Gdn-NS) using first-principles calculation. The Gdn-NS possesses the energy gap value of 0.52 eV. Also, the binding of sorafenib and regorafenib drugs have been studied by adsorption energy, charge transfer including energy gap variation. Also, the quantum molecular descriptor (QMD) such as chemical hardness, electrophilicity, and electronic chemical potential of sorafenib and regorafenib drugs on graphdiyne complex are explored. The density of states (DOS) spectrum shows the deviation in the spectrum peaks upon binding of the drug on graphdiyne sheet. The magnitude of solvation energy is moderate and reveals the solubility of the proposed drugs in the water medium. The sorafenib and regorafenib drug release to the expected target cell is studied based on protonation. Upon protonation of sorafenib and regorafenib drugs, the bond became a weak hydrogen type bond between graphdiyne sheet and drugs and released to the target cell. The findings of the proposed research reveal that the Gdn-NS can be used as a drug carrier vehicle to administer the drug to cancer affected cells.

Graphdiyne Electrocatalyst

Graphdiyne Electrocatalyst