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.

Interfacial Evolution of the Solid Electrolyte Interphase and Lithium Deposition in Graphdiyne-Based Lithium-Ion Batteries.

All-carbon graphdiyne (GDY)-based materials have attracted extensive attention owing to their extraordinary structures and outstanding performance in electrochemical energy storage. Straightforward insights into the interfacial evolution at GDY electrode/electrolyte interface could crucially enrich the fundamental comprehensions and inspire targeted regulations. Herein, in situ optical microscopy and atomic force microscopy monitoring of the GDY and N-doped GDY electrodes reveal the interplay between the solid electrolyte interphase (SEI) and Li deposition. The growth and continuous accumulation of the flocculent-like SEI is directly tracked at the surface of GDY electrode. Moreover, the nanoparticle-shaped SEI homogeneously propagates at the interface when N configurations are involved, providing a critical clue for the N-doping effects of stabilizing interfaces and homogenizing Li deposition. This work probes into the dynamic evolution and structure-reactivity correlation in detail, creating effective strategies for GDY-based materials optimization in lithium-ion batteries.

Stabilizing Interface pH by N-Modified Graphdiyne for Dendrite-Free and High-Rate Aqueous Zn-Ion Batteries.

Zn dendrite issue was intensively studied via tuning zinc ion flux. pH change seriously influences dendrite formation, while its importance has not been revealed. Here, we construct a N-modification graphdiyne interface (NGI) to stabilize pH by mediating hydrated zinc ion desolvation. Operando pH detection reveals pH stabilization by NGI. This works with pores in NGI to achieve dendrite-free Zn deposition and an increased symmetric cell lifespan by 116 times. Experimental and theoretical results owe pH stabilization to desolvation with a reduced activation energy achieved by electron transfer from solvation sheath to N atom. The efficient desolvation ensures that electron directly transfers from substrate to Zn2+ (rather than the coordinated H2 O), avoiding O-H bond splitting. Hence, Zn-V6 O13 battery achieves a long lifespan at 20.65 mA cm-2 and 1.07 mAh cm-2 . This work reveals the significance of interface pH and provides a new approach to address Zn dendrite issue.

High Voltage-Stabilized Graphdiyne Cathode Interface.

Suppressing the irreversible interfacial reactions is an important scientific bottleneck in the development of stable high-energy-density lithium-ion battery. The interfacial chemistry of graphdiyne (GDY) on the high-voltage cathode of LiNi0.5 Mn1.5 O4 (LNMO) shows a very interesting process, in which the sp-hybridization carbon atoms chemically scavenge the hydrofluoric acid (HF) and in situ form the fluorinated GDY interface. It first turns the harmful HF into profit, and greatly enhances the interfacial stability and restrains the side reaction on the cathode under high working voltage. The GDY-coated LNMO cathode obviously alleviates the electrolyte degradation, achieves high Coulombic efficiency and reliability. Due to atomic-level selectivity and chemical trapping of HF by GDY, it effectively suppresses the dissolution of Mn, Ni elements. These results highlight the unparalleled advantages of GDY in the formation of high stable interfaces and protection of high-energy-density electrodes.

High Quality Pyrazinoquinoxaline-Based Graphdiyne for Efficient Gradient Storage of Lithium Ions.

N-doping of graphdiyne with atomic precision is very important for the study of heteroatom doping effect and the structure-properties relationships of graphdiyne. Here we report the bottom-up synthesis and characterizations of high-quality pyrazinoquinoxaline-based graphdiyne (PQ-GDY) film. First-principle studies of the layered structure were performed to examine the stacking mode, lithium binding affinity, and bulk lithium storage capacity. Three-stage insertion of 14 lithium atoms with binding affinities in the order of pyrazine nitrogen > diyne carbon > central aromatic ring were confirmed by both lithium-ion half-cell measurements and DFT calculations. More than half of the lithium atoms preferentially bind to pyrazine nitrogen, and a reversible capacity of 570.0 mA h g-1 at a current density of 200 mA g-1 after 800 cycles was achieved. Such a high capacity utilization rate of 97.2% provides a good case study of N-doped GDY with atomic precision.

N-Doped Graphdiyne Coating for Dendrite-Free Lithium Metal Batteries.

Nonuniform nucleation is one of the major reasons for the dendric growth of metallic lithium, which leads to intractable problems in the efficiency, reversibility, and safety in Li-based batteries. To improve the deposition of metallic Li on Cu substrates, herein, a freestanding current collector (NGDY@CuNW) is formed by coating pyridinic nitrogen-doped graphdiyne (NGDY) nanofilms on 3D Cu nanowires (CuNWs). Theoretical predictions reveal that the introduction of nitrogen atoms in the 2D GDY can enhance the binding energy between the Li atom and GDY, therefore improving the lithiophilicity on the surface for uniform lithium nucleation and deposition. Accordingly, the deposited metallic Li on the NGDY@CuNW electrode exhibits a dendrite-free morphology, resulting in significant improvements in terms of the reversibility with a high coulombic efficiency (CE) and a long lifespan at high current density. Our research provides an efficient method to control the surface property of Cu, which also will be instructive for other metal batteries.

Progress in Research into 2D Graphdiyne-Based Materials.

Graphynes (GYs) are carbon allotropes with single-atom thickness that feature layered 2D structure assembled by carbon atoms with sp - and sp2 - hybridization form. Various functional theories have predicted GYs to have natural band gap with Dirac cones structure, presumably originating from inhomogeneous π-bonding between those carbon atoms with different hybridization and overlap of the carbon 2p z orbitals. Among all the GYs, graphdiyne (GDY) was the first reported to be prepared practically and, hence, attracted the attention of many researchers toward this new planar, layered material, as well as other GYs. Several approaches have been reported to be able to modify the band gap of GDY, containing invoking strain, boron/nitrogen doping, nanoribbon architectures, hydrogenation, and so on. GDY has been well-prepared in many different morphologies, like nanowires, nanotube arrays, nanowalls, nanosheets, ordered stripe arrays, and 3D framwork. The fascinating structure and electronic properties of GDY make it a potential candidate carbon material with many applications. It has recently revealed the practicality of GDY as catalyst; in rechargeable batteries, solar cells, electronic devices, magnetism, detector, biomedicine, and therapy; and for gas separation as well as water purification.

Controllable Synthesis of Graphdiyne Nanoribbons.

Graphdiyne nanoribbons with high chemical precision are of great significance for further understanding of the intrinsic properties of graphdiyne and the relationship between structure and properties. However, the reliable synthesis of graphdiyne nanoribbons with chemical precision remains a significant challenge. A facile method is now presented for fabrication of graphdiyne nanoribbons with uniform width through stepwise inter- and intramolecular Glaser-Hay coupling reaction of ethynyl groups. The synthetic ribbons were interwoven into nanotextiles by π-π stacking and were applied for protective coating of Li-electrode in Li-ion batteries, which efficiently suppressed the growth of the Li dendrites during cycling and prolonged the life span of Li-metal batteries.

Large-Area Aminated-Graphdiyne Thin Films for Direct Methanol Fuel Cells.

A two-dimensional (2D) carbon nanofilm with uniform artificial nanopores is an ideal material to ultimately suppress the fuel permeation in the proton exchange membrane fuel cells. Graphdiyne has great mechanical strength, high dimensional stability, and controllable nanopores, and has good prospects to play this crucial role. It is found that graphdiyne nanofilm with amino groups and natural nanopores can be easily prepared with high integrity. The aminated graphdiyne has good compatibility with the Nafion matrix owing to the acid-base interaction between them. The excellent comprehensive properties of graphdiyne in selectivity, dimensional stability, and integrity effectively improve the power performance and stability of fuel cells at wide temperature. Our results can be developed into a universal method that can easily realize the selective separation of ions and small molecules, and open a new way for the emerging applications in green energy.

Synthesis and Properties of 2D Carbon-Graphdiyne.

Graphdiyne (GDY) is a flat material comprising sp2- and sp-hybridized carbon atoms with high degrees of π conjugation that features uniformly distributed pores. It is interesting not only from a structural point of view but also from the perspective of its electronic, chemical, mechanical, and magnetic properties. We have developed an in situ homocoupling reaction of hexaethynylbenzene on Cu foil for the fabrication of large-area ordered films of graphdiyne. These films are uniform and composed of graphdiyne multilayers. The conductivity of graphdiyne films, calculated at 2.52 × 10-4 S m-1, is comparable to that of Si, suggesting excellent semiconducting properties. Through morphology-controlled syntheses, we have prepared several well-defined graphdiyne structures (e.g., nanotubes, nanowires, and nanowalls) having distinct properties. The graphdiyne nanotube arrays and graphdiyne nanowalls exhibited excellent field emission performance, higher than that of some other semiconductors such as graphite and carbon nanotubes. These structures have several promising applications, for example, as energy storage materials and as anode materials in batteries. The unique atomic arrangement and electronic structure of graphdiyne also inspired us to use it to develop highly efficient catalysts; indeed, its low reduction potential and highly conjugated electronic structure allow graphdiyne to be used as a reducing agent and stabilizer for the electroless deposition of highly dispersed and surfactant-free Pd clusters. GDY-based three-dimensional (3D) nanoarchitectures featuring well-defined porous network structures can function as highly active cathodes for H2 evolution. Heteroatom-doped GDY structures are excellent metal-free electrocatalysts for the oxygen reduction reaction (ORR). Its excellent electrocatalytic activity and inexpensive, convenient, and scalable preparation make GDY a promising candidate for practical and efficient energy applications; indeed, we have explored the application of GDY as a highly efficient lithium storage material and have elucidated the method through which lithium storage occurs in multilayer GDY. Lithium-ion batteries featuring GDY-based electrodes display excellent electrochemical performance, including high specific capacity, outstanding rate performance, and long cycle life. We have also explored the application of GDY in energy conversion and found that it exhibits excellent conductivity. In this Account, we summarize the relationships between the functions of graphdiyne and its well-defined nanostructures. Our results suggest that GDY is a novel 2D carbon material possessing many attractive properties. It can be designed into new nanostructures and materials across a range of compositions, sizes, shapes, and functionalities and can be applied in the fields of electronics, optics, energy, and optoelectronics.

Ultrathin Graphdiyne Nanosheets Grown In†Situ on Copper Nanowires and Their Performance as Lithium-Ion Battery Anodes.

A method is presented for the scalable preparation of high-quality graphdiyne nanotubes and ultrathin graphdiyne nanosheets (average thickness: ca. 1.9 nm) using Cu nanowires as a catalyst. For the storage of Li+ ions, the graphdiyne nanostructures show a high capacity of 1388 mAh g-1 and high rate performance (870 mA h g-1 at 10 A g-1 , and 449.8 mA h g-1 at 20 A g-1 ) with robust stability, demonstrating outstanding overall potential for its applications.

Graphdiyne-Supported NiCo2 S4 Nanowires: A Highly Active and Stable 3D Bifunctional Electrode Material.

The oxygen evolution reaction (OER), hydrogen evolution reaction (HER), and overall water splitting are major energy and chemical conversion efforts. Progress in electrocatalytic reactions have shown that the future is limitless in many fields. However, it is urgent to develop efficient electrocatalysts. Here, the first graphdiyne-supported efficient and bifunctional electrocatalyst is reported using 3D graphdiyne foam as scaffolds, and NiCo2 S4 nanowires as building blocks (NiCo2 S4 NW/GDF). NiCo2 S4 NW/GDF exhibits outstanding catalytic activity and stability toward both OER and HER, as well as overall water splitting in alkaline media. Remarkably, it enables a high-performance alkaline water electrolyzer with 10 and 20 mA cm-2 at very low cell voltages of 1.53 and 1.56 V, respectively, and remarkable stability over 140 h of continuous electrolysis operation at 20 mA cm-2 . The results indicate that this catalyst has a bifunction that overcomes all reported bifunctional, nonprecious-metal-based ones.

Ultra-light Hierarchical Graphene Electrode for Binder-Free Supercapacitors and Lithium-Ion Battery Anodes.

A mild and environmental-friendly method is developed for fabricating a 3D interconnected graphene electrode with large-scale continuity. Such material has interlayer pores between reduced graphene oxide nanosheets and in-plane pores. Hence, a specific surface area up to 835 m(2) g(-1) and a high powder conductivity up to 400 S m(-1) are achieved. For electrochemical applications, the interlayer pores can serve as "ion-buffering reservoirs" while in-plane ones act as "channels" for shortening the mass cross-plane diffusion length, reducing the ion response time, and prevent the interlayer restacking. As binder-free supercapacitor electrode, it delivers a specific capacitance up to 169 F g(-1) with surface-normalized capacitance close to 21 µF cm(-2) (intrinsic capacitance) and power density up to 7.5 kW kg(-1), in 6 m KOH aqueous electrolyte. In the case of lithium-ion battery anode, it shows remarkable advantages in terms of the initiate reversible Coulombic efficiency (61.3%), high specific capacity (932 mAh g(-1) at 100 mA g(-1)), and robust long-term retention (93.5% after 600 cycles at 2000 mAh g(-1)).

Self-Adaptive Graphdiyne/Sn Interface for High-Performance Sodium Storage.

Efficiently reconciling the substantial volume strain with maintaining the stabilities of both interfacial protection and three-dimensional (3D) conductive networks is a scientific and technical challenge in developing tin-based anodes for sodium ion storage. To address this issue, a proof-of-concept self-adaptive protection for the Sn anode is designed, taking advantage of the arbitrary substrate growth of graphdiyne. This protective layer, employing a flexible chain doping strategy, combines the benefits of 2D graphdiyne and linear chain structures to achieve 2D mechanical stability, electronic and ion conductions, ion selectivity, adequate elongation, and flexibility. It establishes close contact with the Sn particles and can adapt to dynamic size changes while effectively facilitating both electronic and ion transports. It successfully mitigates the detrimental effects of particle pulverization and coarsening induced by large-volume changes. The as-obtained Sn electrodes demonstrate exceptional stability, enduring 1800 cycles at a high current density of 2.5 A g-1. This strategy promises to address the general issues associated with large-strain electrodes in next-generation of high-energy-density batteries.

Ultrathin graphdiyne nanosheets confining Cu quantum dots as robust electrocatalyst for biosensing featuring remarkably enhanced activity and stability.

There is an urgent need for developing electrochemical biosensor based on the acetylcholinesterase (AChE) inhibition to real-time analysis of organophosphorus pesticides (OPs), but it is suffered from the sluggish electrode kinetics and high oxidation potential toward signal species. Herein, a nanocomposite of ultrafine Cu quantum dots (QD) uniformly loaded on three-dimensional ultrathin graphdiyne (GDY) nanosheets (denoted as Cu@GDY) was synthesized via a one-step strategy, which showing high-density of active sites with persistent stability. Then an AChE biosensor based on Cu@GDY was fabricated to detect OPs, and the results revealed that the Cu@GDY nanocomposite can significantly amplifies electrochemical signal and reduces the oxidation potential for OPs. The strong interaction between active site of Cu@GDY and thiocholine signal species caused rapid analyte aggregation and decreased the reaction activation energy of thiocholine electro-oxidation. Benefiting from the excellent catalytic activity of Cu@GDY nanocomposite and reasonable regulation of enzyme inhibition kinetics, the biosensor achieved rapid and sensitive detection of OPs with a detection limit of 1 µg L-1 for paraoxon. Furthermore, the biosensor demonstrated great reproducibility, good stability and high recovery rate for OPs detection in real samples. Cu@GDY based sensor also displayed high catalytic activities and good selectivity to the non-enzymatic detection of glucose in alkaline medium. Cu@GDY offers a versatile and promising platform for sensors and biosensors featuring remarkably enhanced activity and stability, and can be applied to many other fields as desirable electrocatalyst.

High energy density primary cathode with a mixed electron/ion interface.

An effective and original strategy described as two-dimensional encapsulation is designed to prepare a high-performance fluorinated carbon cathode composed of a fluorinated carbon/graphdiyne heterostructure (CFx/GDY). The GDY layers of CFx/GDY strengthened the three-dimensional contacts between the CFx particles and additive, achieving outstanding charge transport kinetics and accelerating the lithium-ion diffusion dynamic behavior. The obtained electrodes exhibited a significantly enhanced voltage platform of ∼2.5 V, improved battery rate performance (5C, 621.6 mA h g-1) and energy density with 2039.3 W h kg-1. The excellent storage kinetics can be ascribed to the electronic structure modulation of fluorinated carbon from GDY, and the hierarchical porosity of GDY to create an effective, stable electron transfer and robust ion transportation. Our results demonstrated that two-dimensional GDY encapsulation has enormous potential in improving the performance of lithium primary batteries.

Controlled Growth of 3D Interpenetrated Networks by NiCo2O4 and Graphdiyne for High-Performance Supercapacitor.

In this paper, the 2D all-carbon graphdiyne, which possesses superior 2D strength and high mixed conductivities for both electrons and ions, is used to protect nickel cobalt oxide nanostructures with multidimensions. The in situ grown graphdiyne seamlessly wraps on nanostructures to form 3D interpenetrating networks, leading to significant improvement in the conductivity and avoidance of the structural degradation. The assembled hybrid asymmetric supercapacitor showed a high specific capacitance of 200.9 F g-1 at 1 A g-1 with an energy density of 62.8 Wh kg-1 and a power density of 747.9 W kg-1. The device also showed a preeminent rate capability (86.4% capacitance retention, while the current density was increased from 1 to 20 A g-1) and an ultrastable long-term cycling performance (the capacitance retention is about 97.7% after 10 000 cycles at a high current density of 20 A g-1).

Synthesis of a [2]rotaxane incorporating a "magic sulfur ring" by the thiol-ene click reaction.

The mild and highly efficient thiol-ene click reaction has been used to construct a rotaxane incorporating dibenzo-24-crown-8 (DB24C8) and a dibenzylammonium-derived thread in high yield under the irradiation of UV light. A rotaxane containing a disulfide linkage in the macrocycle was also synthesized by the thiol-ene click reaction. It has been demonstrated that the formation of the [2]rotaxane with the disulfide bond in the macrocycle occurs by a mechanism that is different to the threading-followed-by-stoppering process. The successful construction of a rotaxane directly from its constituent components, the macrocycle containing a disulfide linkage and the dibenzylammonium hexafluorophosphate salt, suggests that the space within the macrocycle incorporating the disulfide linkage is smaller than the phenyl unit and a plausible reaction mechanism has been proposed as follows: A small amount of the initiator forms two radicals upon the absorption of UV irradiation; the radicals act as a "key" to "unlock" the disulfide bond in the macrocycle. The resulting crown ether like moiety in the macrocycle is clipped around the ammonium ion center in the dumb-bell-shaped compound. The [2]rotaxane is generated upon recombination of the disulfide linkage.

Crystalline Fully Carboxylated Polyacetylene Obtained under High Pressure as a Li-Ion Battery Anode Material.

Substituted polyacetylene is expected to improve the chemical stability, physical properties, and combine new functions to the polyacetylene backbones, but its diversity is very limited. Here, by applying external pressure on solid acetylenedicarboxylic acid, we report the first crystalline poly-dicarboxylacetylene with every carbon on the trans-polyacetylene backbone bonded to a carboxyl group, which is very hard to synthesize by traditional methods. The polymerization is evidenced to be a topochemical reaction with the help of hydrogen bonds. This unique structure combines the extremely high content of carbonyl groups and high conductivity of a polyacetylene backbone, which exhibits a high specific capacity and excellent cycling/rate performance as a Li-ion battery (LIB) anode. We present a completely functionalized crystalline polyacetylene and provide a high-pressure solution for the synthesis of polymeric LIB materials and other polymeric materials with a high content of active groups.

Spontaneously Splitting Copper Nanowires into Quantum Dots on Graphdiyne for Suppressing Lithium Dendrites.

As an emerging carbon allotrope, the controllable growth of graphdiyne has been an important means to explore its unique scientific properties and applications. In this work, the effect of the crystal structure of copper (Cu) on the growth of graphdiyne is systematically studied. It is found that the crystal boundaries are the origin of the reaction activity. The polycrystalline Cu nanowire with many crystal boundaries is spontaneously split into Cu quantum dots (about 3 nm) by the grown graphdiyne. These Cu quantum dots are uniformly dispersed on the graphdiyne, and they block the long-range ordered growth of the graphdiyne. These Cu quantum dots in situ supported on graphdiyne demonstrate high efficiency in inhibiting the growth of lithium dendrites in lithium metal batteries. Based on this interesting finding, the Cu quantum dots anchored on the all-carbon graphdiyne can be prepared on a large scale, and unique applications of Cu quantum dots in electrochemical fields can be implemented.