Structure Of Graphdiyne Research Articles

In situ proof construction of GDY/NiWO4/CdS double S-scheme heterojunction: Improving charge transfer and promoting photocatalytic activity

In the field of photocatalysis, the inherent properties of catalysts are a hard condition that affects catalytic performance, and constructing heterojunctions is a common method to improve catalyst defects and enhance catalyst performance. This article makes effective use of the outstanding stability and unique electronic structure of graphdiyne, along with its excellent semiconductor properties comparable to silicon. It uses these properties to attach rod-shaped CdS and microspherical NiWO4 onto sheet-like graphdiyne, creating an S-scheme heterojunction. With the construction of S-scheme heterojunctions and the special contact methods between the three, the physical potential barrier and the distance of electron transfer are reduced. Furthermore, the combined impact of NiWO4 and graphdiyne works to inhibit the photo corrosion of CdS, enhance its electron transfer capabilities, decrease electron-hole recombination efficiency, and boost hydrogen evolution sites. This maximizes the redox potential during catalysis, leading to exceptional stability and efficiency of the composite catalyst. This study opens up a new avenue for leveraging the superior properties of graphdiyne and advancing sustainable practices.

Graphdiyne Preparation and Application in Photocatalytic Hydrogen Evolution.

Graphdiyne (GDY) is a new two-dimensional carbon network material composed of sp2 hybrid carbon and sp hybrid carbon conjugation. It has unique physical and chemical properties, such as high porosity, good electrical conductivity, high carrier mobility, adjustable band gap, and so on. The preparation of GDY and GDY derivatives by adjusting physical and chemical methods and changing monomers has become the key material in the fields of photocatalysis, energy storage, life science, and so on. In this paper, new methods for controllable growth of GDY are reviewed, including liquid phase chemical classical total synthesis, chemical vapor deposition, the interface method, the explosion method, and the mechanically driven ball milling method. FT-IR, Raman, NMR, and XAS are the main means to characterize the structure of GDY. Finally, the representative application of GDY in the field of photocatalytic hydrogen evolution is summarized, and its future development has been explored.

Application of graphdiyne for promote efficient photocatalytic hydrogen evolution

The photocatalytic hydrogen evolution technology converts solar energy into clean and environmentally friendly hydrogen energy, which is considered an effective means to solve environmental pollution and energy crisis. The unique sp and sp2 hybrid carbon network structure of graphdiyne endows it with excellent carrier mobility, and high porosity, making it a promising photocatalytic material for solar energy conversion. This article provides a detailed description of the unique structural properties and adjustable bandgap of graphdiyne. In addition, a detailed review was provided on the modification strategies of graphdiyne based catalysts for photocatalytic hydrogen evolution, including titanium based photocatalysts, metal oxide photocatalysts, double hydroxide catalysts, metal organic framework photocatalysts and other typical semiconductors. Finally, the challenges and opportunities for developing graphdiyne semiconductors for photocatalytic water splitting were proposed. Timely review is expected to contribute to the rapid development of graphdiyne in the field of photocatalytic hydrogen evolution.

Rational design of graphdiyne-based single-atom catalysts for electrochemical CO2 reduction reaction.

Graphdiyne (GDY) has achieved great success in the application of two-dimensional carbon materials in recent years due to its excellent electrochemical catalytic capacity. Considering the unique electronic structure of GDY, transition metal (TM1) (TM = Fe, Ru, Os, Co, Rh, Ir) single-atom catalysts (SACs) with isolated loading on GDY were designed for electrochemical CO2 reduction reaction (CO2RR) with density functional theoretical (DFT) calculations. The charge density difference and projected densities of states have been systematically calculated. The mechanism of electrochemical catalysis and the reaction pathway of CO2RR over Os1/GDY catalysts have also been investigated and high catalytic activity was found for the generation of methane. The calculated results provide a theoretical basis for the design of efficient GDY-based SACs for electrochemical CO2RR.

Structural identification of single boron-doped graphdiynes by computational XPS and NEXAFS spectroscopy.

Boron-doped graphdiyne (B-GDY) material exhibits an excellent performance in electrocatalysis, ion transport, and energy storage. However, accurately identifying the structures of B-GDY in experiments remains a challenge, hindering further selection of suitable structures with the most ideal performance for various practical applications. In the present work, we employed density functional theory (DFT) to simulate the X-ray photoelectron spectra (XPS) and near-edge X-ray absorption fine-structure (NEXAFS) spectra of pristine graphdiyne (GDY) and six representative single boron-doped graphdiynes at the B and C K-edges to establish the structure-spectroscopy relationship. A notable disparity in the C 1s ionization potentials (IPs) between substituted and adsorbed structures is observed upon doping with a boron atom. By analyzing the C and B 1s NEXAFS spectra on energy positions, spectral widths, spectral intensities, and different spectral profiles, we found that the six single boron-doped graphdiyne configurations can be sensitively identified. Moreover, this study provides a reliable theoretical reference for distinguishing different single boron-doped graphdiyne structures, enabling accurate selection of B-GDY structures for diverse practical applications.

Enhanced kinetics of photocatalytic hydrogen evolution by interfacial Co-C bonded strongly coupled S-scheme inorganic perovskite/organic graphdiyne (CnH2n-2) heterojunction

The special intrinsic properties and structure of graphdiyne (GDY) bring new space for innovation in the field of photocatalysis. In this work, we utilized the in-situ high-temperature calcination strategy to induce the formation of Co-C chemical bonds at the interface of the catalyst and tightly bound organic GDY to inorganic perovskite CoTiO3 to form an S-scheme heterojunction with strong coupling of chemical bonds. Co-C chemically bonded strongly coupled S-scheme heterojunctions play an active role in promoting the effective separation of photo-induced carriers, lowering the hydrogen generation potential, reducing the resistance to photo-induced electron migration, delaying the lifetime of photogenerated electrons, and enhancing the photo-reduction ability. Kelvin probe force microscopy verifies the formation of built-in electric fields at the heterojunction interface. In situ irradiation XPS to verify the formation of S-scheme heterojunctions base on DFT as a guide for the theory and photo-Tafel as an aid. The in-situ irradiation XPS in-depth study and Kelvin probe force microscopy reveals the migration path of photogenerated carriers in 20%-GCTO. Among them, the introduction of Co-C chemical bond plays the role of a high-speed transfer channel for the migration of photogenerated electrons. This work provides a new strategy for designing in situ induced interfacial covalent bond formation in S-scheme heterojunctions and constructing inorganic/organic heterojunctions.

Graphdiyne (CnH2n−2)/NiWO4 self-assembled p–n junction characterized with in situ XPS for efficient photocatalytic hydrogen production

As is well known, how to deeply understand the charge separation and charge transfer capabilities of catalysts, as well as how to optimize these capabilities of catalysts to improve hydrogen production performance, remains a huge challenge. In recent years, a new type of carbon material graphdiyne (GDY) has been proposed. GDY acetylene has a special atomic arrangement that graphene does not have a two-dimensional network of sp2 and sp conjugated intersections makes it easier to construct active sites and improve photocatalytic ability. In addition, GDY also has the advantage of adjusting the bandgap of other catalysts and inhibiting carrier recombination, making it more prone to hydrogen evolution reactions. In addition to using mechanical ball milling to produce GDY, NiWO4 without precious metals was also prepared. The sheet-like structure of GDY in the composite catalyst provides a anchoring site and more active sites for the granular NiWO4. And the composite catalyst fully enhances the good conductivity of GDY and its unique ability to enhance electron transfer, greatly improving the ability of NiWO4 as a single substance. Through in-situ x-ray photoelectron spectrometer, it was demonstrated that a p–n heterojunction was constructed between GDY and NiWO4 in the composite catalyst, further enhancing the synergistic effect between the two, resulting in a hydrogen production rate of 90.92 μmol for the composite catalyst is 4.56 times higher than that of GDY and 4.97 times higher than that of NiWO4, respectively, and the stability of the composite catalyst is significantly higher than that of each single catalyst.

Two-Dimensional Carbon Graphdiyne: Advances in Fundamental and Application Research.

Graphdiyne (GDY), a rising star of carbon allotropes, features a two-dimensional all-carbon network with the cohybridization of sp and sp2 carbon atoms and represents a trend and research direction in the development of carbon materials. The sp/sp2-hybridized structure of GDY endows it with numerous advantages and advancements in controlled growth, assembly, and performance tuning, and many studies have shown that GDY has been a key material for innovation and development in the fields of catalysis, energy, photoelectric conversion, mode conversion and transformation of electronic devices, detectors, life sciences, etc. In the past ten years, the fundamental scientific issues related to GDY have been understood, showing differences from traditional carbon materials in controlled growth, chemical and physical properties and mechanisms, and attracting extensive attention from many scientists. GDY has gradually developed into one of the frontiers of chemistry and materials science, and has entered the rapid development period, producing large numbers of fundamental and applied research achievements in the fundamental and applied research of carbon materials. For the exploration of frontier scientific concepts and phenomena in carbon science research, there is great potential to promote progress in the fields of energy, catalysis, intelligent information, optoelectronics, and life sciences. In this review, the growth, self-assembly method, aggregation structure, chemical modification, and doping of GDY are shown, and the theoretical calculation and simulation and fundamental properties of GDY are also fully introduced. In particular, the applications of GDY and its formed aggregates in catalysis, energy storage, photoelectronic, biomedicine, environmental science, life science, detectors, and material separation are introduced.

A Low‐Strain Cathode by sp‐Carbon Induced Conversion in Multi‐Level Structure of Graphdiyne

AbstractA multi‐level architecture formed alternatively by the conformal graphdiyne (GDY) and CuS is well engineered for Li‐free cathode. Such a proof‐of‐concept architecture efficiently integrates the advantages of GDY and produces new functional heterojunctions (sp−C−S−Cu hybridization bond). The layer‐by‐layer 2D confinement effect successfully avoids structural collapse, the selective transport inhibits the shuttling of active components, and the interfacial sp−C−S−Cu hybridization bond significantly regulates the phase conversion reaction. Such new sp−C−S−Cu hybridization of GDY greatly improves the reaction dynamics and reversibility, and the cathode delivers an energy density of 934 Wh kg−1 and an unattenuated lifespan of 3000 cycles at 1 C. Our results indicate that the GDY‐based interface strategy will greatly promote the efficient utilization of the conversion‐type cathodes.

A Low-Strain Cathode by sp-Carbon Induced Conversion in Multi-Level Structure of Graphdiyne.

A multi-level architecture formed alternatively by the conformal graphdiyne (GDY) and CuS is well engineered for Li-free cathode. Such a proof-of-concept architecture efficiently integrates the advantages of GDY and produces new functional heterojunctions (sp-C-S-Cu hybridization bond). The layer-by-layer 2D confinement effect successfully avoids structural collapse, the selective transport inhibits the shuttling of active components, and the interfacial sp-C-S-Cu hybridization bond significantly regulates the phase conversion reaction. Such new sp-C-S-Cu hybridization of GDY greatly improves the reaction dynamics and reversibility, and the cathode delivers an energy density of 934 Wh kg-1 and an unattenuated lifespan of 3000 cycles at 1 C. Our results indicate that the GDY-based interface strategy will greatly promote the efficient utilization of the conversion-type cathodes.

Rationally engineered active site over graphdiyne (CnH2n-2) based S-scheme heterojunction for efficient and durable hydrogen production

The strategy of based on graphdiyne constructing S-scheme heterostructure building electron bridge by inducing Co-P bond through high-temperature phosphorylation. At the interface between CuCo2O4 and graphdiyne, the Co-P bond constructs the electron bridge, which inhibits photogenic carrier recombination and weak light absorption performance of the original CuCo2O4. The lamellar structure of graphdiyne was anchored on the surface of nanospheres, which not only increased the surface ratio, but also provided conditions for graphdiyne to be used as an active site for hydrogen evolution. The experimental and DFT results show that the increase of CoP nanoparticles is conducive to the formation of abundant Co-P bonds, and thus the formation of “electron Bridges”, which can accelerate the transfer of photoelectrons and improve the photocatalytic hydrogen production performance. In addition, P-GC25-11 showed excellent hydrogen production performance in the photocatalytic experiment. The photocatalytic hydrogen evolution activity of P-GC25-11 was 219.11 mmol, 7.8 times that of CuCo2O4 and 52 times that of graphdiyne, respectively. This strategy opens up a new way for the baize of construction of S-scheme heterojunctions based on graphdiyne, and constructing the “electron bridge” to accelerate the transfer of photogenerated electrons, thus improving the activity of photocatalytic hydrogen production.

Synthesis of Graphdiyne Hollow Spheres and Multiwalled Nanotubes and Applications in Water Purification and Raman Sensing.

Controlling the structure of graphdiyne (GDY) is crucial for the discovery of new properties and the development of new applications. Herein, the microemulsion synthesis of GDY hollow spheres (HSs) and multiwalled nanotubes composed of ultrathin nanosheets is reported for the first time. The formation of an oil-in-water (O/W) microemulsion is found to be a key factor controlling the growth of GDY. These GDY HSs have fully exposed surfaces because of the avoidance of overlapping between nanosheets, thereby showing an ultrahigh specific surface area of 1246 m2 g-1 and potential applications in the fields of water purification and Raman sensing.

Second Sphere Effects Promote Formic Acid Dehydrogenation by a Single‐Atom Gold Catalyst Supported on Amino‐Substituted Graphdiyne

AbstractRegulating the second sphere of homogeneous molecular catalysts is a common and effective method to boost their catalytic activities, while the second sphere effects have rarely been investigated for heterogeneous single‐atom catalysts primarily due to the synthetic challenge for installing functional groups in their second spheres. Benefiting from the well‐defined and readily tailorable structure of graphdiyne (GDY), an Au single‐atom catalyst on amino‐substituted GDY is constructed, where the amino group is located in the second sphere of the Au center. The Au atoms on amino‐decorated GDY displayed superior activity for formic acid dehydrogenation compared with those on unfunctionalized GDY. The experimental studies, particularly the proton inventory studies, and theoretical calculations revealed that the amino groups adjacent to an Au atom could serve as proton relays and thus facilitate the protonation of an intermediate Au−H to generate H2. Our study paves the way to precisely constructing the functional second sphere on single‐atom catalysts.

Second Sphere Effects Promote Formic Acid Dehydrogenation by a Single-Atom Gold Catalyst Supported on Amino-Substituted Graphdiyne.

Regulating the second sphere of homogeneous molecular catalysts is a common and effective method to boost their catalytic activities, while the second sphere effects have rarely been investigated for heterogeneous single-atom catalysts primarily due to the synthetic challenge for installing functional groups in their second spheres. Benefiting from the well-defined and readily tailorable structure of graphdiyne (GDY), an Au single-atom catalyst on amino-substituted GDY is constructed, where the amino group is located in the second sphere of the Au center. The Au atoms on amino-decorated GDY displayed superior activity for formic acid dehydrogenation compared with those on unfunctionalized GDY. The experimental studies, particularly the proton inventory studies, and theoretical calculations revealed that the amino groups adjacent to an Au atom could serve as proton relays and thus facilitate the protonation of an intermediate Au-H to generate H2. Our study paves the way to precisely constructing the functional second sphere on single-atom catalysts.

Construction of graphdiyne (CnH2n-2) based Co-S-P/CuI double S-scheme heterojunctions proved with in situ XPS characterization for efficient photocatalytic hydrogen production

Graphdiyne (GDY) is a novel two-dimensional carbon isomeric material with a high π⁃conjugation and good electrical conductivity, a tunable natural band gap. Here, the promotion of GDY on the photocatalytic system is investigated by preparing Co-S-P/CuI double S-scheme heterojunctions based on graphdiyne (CnH2n-2). The Co-S-P rough nanosheet structure provides a large number of aiming points for CuI nanoblocks, which effectively prevents the aggregation of CuI nanoblocks. It not only provides a large number of active sites for the reaction, but also facilitates the visible light injection. When GDY is introduced, the three-dimensional structure of GDY/CuI is tightly attached to the Co-S-P surface. On the one hand, the unique two-dimensional/three-dimensional structure is beneficial to promote the mass transfer properties between Co-S-P, GDY and CuI and improve the absorption of visible light. On the other hand, the unique lamellar structure of GDY is like a “tape” connecting Co-S-P and CuI, which not only makes the bond between Co-S-P and CuI tighter, but also serves as a “fabric” to isolate the oxidation sites on the surface of Co-S-P. As a result, the ternary catalyst exhibits excellent hydrogen precipitation stability and photocorrosion resistance. Under 5 W (λ > 420 nm) LED light, CSPGC-20 (135.49 μmol) exhibited the best hydrogen precipitation activity, which is 26.22, 9.2 and 1.6 times higher than that of GDY/CuI (5.32 μmol), Co-S-P (14.72 μmol) and CSPC-20 (85.08 μmol), respectively. This experiment demonstrates the promising potential of Graphdiyne (GDY) for photocatalytic water splitting.

Electronic Perturbation of Copper Single‐Atom CO2Reduction Catalysts in a Molecular Way

AbstractFine‐tuning electronic structures of single‐atom catalysts (SACs) plays a crucial role in harnessing their catalytic activities, yet challenges remain at a molecular scale in a controlled fashion. By tailoring the structure of graphdiyne (GDY) with electron‐withdrawing/‐donating groups, we show herein the electronic perturbation of Cu single‐atom CO2reduction catalysts in a molecular way. The elaborately introduced functional groups (−F, −H and −OMe) can regulate the valance state of Cuδ+, which is found to be directly scaled with the selectivity of the electrochemical CO2‐to‐CH4conversion. An optimum CH4Faradaic efficiency of 72.3 % was achieved over the Cu SAC on the F‐substituted GDY. In situ spectroscopic studies and theoretical calculations revealed that the positive Cuδ+centers adjusted by the electron‐withdrawing group decrease the pKaof adsorbed H2O, promoting the hydrogenation of intermediates toward the CH4production. Our strategy paves the way for precise electronic perturbation of SACs toward efficient electrocatalysis.

Electronic Perturbation of Copper Single-Atom CO2 Reduction Catalysts in a Molecular Way.

Fine-tuning electronic structures of single-atom catalysts (SACs) plays a crucial role in harnessing their catalytic activities, yet challenges remain at a molecular scale in a controlled fashion. By tailoring the structure of graphdiyne (GDY) with electron-withdrawing/-donating groups, we show herein the electronic perturbation of Cu single-atom CO2 reduction catalysts in a molecular way. The elaborately introduced functional groups (-F, -H and -OMe) can regulate the valance state of Cuδ+ , which is found to be directly scaled with the selectivity of the electrochemical CO2 -to-CH4 conversion. An optimum CH4 Faradaic efficiency of 72.3 % was achieved over the Cu SAC on the F-substituted GDY. In situ spectroscopic studies and theoretical calculations revealed that the positive Cuδ+ centers adjusted by the electron-withdrawing group decrease the pKa of adsorbed H2 O, promoting the hydrogenation of intermediates toward the CH4 production. Our strategy paves the way for precise electronic perturbation of SACs toward efficient electrocatalysis.

Neighbourhood Sum Degree-Based Indices and Entropy Measures for Certain Family of Graphene Molecules

A topological index (TI) is a real number that defines the relationship between a chemical structure and its properties and remains invariant under graph isomorphism. TIs defined for chemical structures are capable of predicting physical properties, chemical reactivity and biological activity. Several kinds of TIs have been defined and studied for different molecular structures. Graphene is the thinnest material known to man and is also extremely strong while being a good conductor of heat and electricity. With such unique features, graphene and its derivatives have found commercial uses and have also fascinated theoretical chemists. In this article, the neighbourhood sum degree-based M-polynomial and entropy measures have been computed for graphene, graphyne and graphdiyne structures. The proper analytical expressions for these indices are derived. The obtained results will enable theoretical chemists to study these exciting structures further from a structural perspective.

Ni/Graphdiyne composites inhibit dendrite growth in lithium metal anodes

The growth of lithium dendrites during repeated deposition or dissolution is a key issue that inhibits lithium metal anodes for high energy density batteries. Here, we demonstrate nickel-anchored graphdiyne materials by solvothermal method on three-dimensional copper foam and apply them to Li metal deposition and stripping. The graphdiyne has a very high Li storage capacity, but poor Li affinity. On the other hand, Ni is highly lithiophilicity and the rich nanoporous structure of graphdiyne provides a stable Li deposition interface, enabling high-efficiency and high-capacity Li deposition and stripping. Ni-anchored graphdiyne modified copper foam substrate can achieve high-area, high-rate dendrite-free Li deposition and stripping. The deposition and stripping of 1 mA h cm−2 of lithium at a current density of 1 mA cm−2 show an overpotential of about 12 mV, high cycle efficiency of 98.5%, and a cycle time of up to 2200 h. The cycle efficiency can reach 98% at higher current density and higher lithium deposition and stripping amount. We assemble a full battery with Ni/GDY@Li using LiFePO4 as the cathode material, showing excellent capacity and cycling stability.

Photoelectrochemical sensor based on carboxylated graphdiyne co-sensitized TiO2 for sensitive detection of dopamine

As a new type of carbon material, graphdiyne (GDY) has wide application prospects in the fields of photocatalysts and photoelectrochemical detection due to its suitable energy bandwidth and high electronic conductivity. However, the highly conjugated and stable macrocyclic structure of GDY makes it difficult to be isomerized and modified on other materials. In this work, click chemistry was used to successfully carboxylate GDY so that it can be stably combined with other optoelectronic materials and some small biological molecules through chemical bonds. A composite optoelectronic material of carboxylated GDY and TiO2 was synthesized and successfully applied in the field of photoelectrochemical detection, a stable and sensitive dopamine sensor was obtained. Based on multiple signal amplification strategy, a wide linear detection range from 0.0005 mM to 1.05 mM with a low detection limit (1.36 × 10−4 mM) was obtained.