Graphynes for Water Desalination and Gas Separation

Selective transport of mass through membranes, so‐called separation, is fundamental to many industrial applications, e.g., water desalination and gas separation. Graphynes, graphene analogs yet containing intrinsic uniformly distributed pores, are excellent candidates for highly permeable and selective membranes owing to their extreme thinness and high porosity. Graphynes exhibit computationally determined separation performance far beyond experimentally measured values of commercial state‐of‐the‐art polyamide membranes; they also offer advantages over other atomically thin membranes like porous graphene in terms of controllability in pore geometry. Here, recent progress in proof‐of‐concept computational research into various graphynes for water desalination and gas separation is discussed, and their theoretically predicted outstanding permeability and selectivity are highlighted. Challenges associated with the future development of graphyne‐based membranes are further analyzed, concentrating on controlled synthesis of graphyne, maintenance of high structural stability to withstand loading pressures, as well asthe demand for accurate computational characterization of separation performance. Finally, possible directions are discussed to align future efforts in order to push graphynes and other 2D material membranes toward practical separation applications.     

One‐Step Preparation of Highly Durable Superhydrophobic Carbon Nanothorn Arrays

This study proposes a one‐step method for growing superhydrophobic carbon nanothorn arrays (NTAs) directly on various substrates. The fabricated carbon material (named methyl‐substituted graphdiyne (MGDY)) comprises sp and sp² carbons in a conjugated‐backbone form, as well as methyl groups introduced into the framework as hydrophobic‐enhanced functional groups. MGDY NTAs exhibit excellent hydrophobicity (contact angle ≥152°), substantial long‐period hydrophobic durability (the contact angle decreased by only 3.2% over 800 days), and acid/alkali tolerance. Owing to the enhanced durability and specific stability of carbon, a superhydrophobic interface can easily be constructed using MGDY NTAs, which can be applied to achieve successful long‐term metal‐corrosion protection and efficient oil–water separation.     

Catalyst‐Free Synthesis of Few‐Layer Graphdiyne Using a Microwave‐Induced Temperature Gradient at a Solid/Liquid Interface

Graphdiyne (GDY), a 2D carbon allotrope, is predicted to possess high carrier mobility and an intrinsic bandgap. However, the controlled synthesis of mono‐ or few‐layer GDY with good crystallinity remains challenging because of the instability of the monomers. Herein, a rapid and catalyst‐free synthetic method is presented for few‐layer GDY involving the use of a solid/liquid interface and a microwave‐induced temperature gradient. Sodium chloride, which can absorb microwave energy, is used as the solid substrate in a nonabsorbing solvent. A temperature gradient is formed at the solid/liquid interface under microwave irradiation, facilitating the cross‐coupling reaction of monomers at the solid surface and stabilizing the monomers in the bulk solution. Few‐layer GDY with an average thickness of less than 2 nm, a field‐effect mobility of 50.1 cm² V^?1 s^?1, and p‐type characteristics is successfully obtained. This wet chemical approach may be extended to the synthesis of other few‐layered 2D materials with improved quality.     

Antibacterial Activity of Graphdiyne and Graphdiyne Oxide

From manufacture to disposal, the interaction of graphdiyne based nanomaterials with living organisms is inevitable and crucial. However, the cytotoxic properties of this novel carbon nanomaterial are rarely investigated, and the mechanisms behind their cytotoxicity are totally unknown. In this study, the antibacterial activity of graphdiyne (GDY) and graphdiyne oxide (GDYO) is reported. GDY is capable of inhibiting broad‐spectrum bacterial growth while exerting moderate cytotoxicity on mammalian cells. In comparison, GDYO exhibits lower antibacterial activity than that of GDY. Then an alterable, synergetic antibacterial mechanism of GDY, involving wrapping bacterial membrane, membrane insertion and disruption, and reactive oxygen species generation is demonstrated, while the differential gene expression analysis indicates that GDY could only alter the bacterial metabolism slightly and the oxidative stress route may be a minor bactericidal factor. The investigation of the antibacterial behaviors of GDY based nanomaterials may provide useful guidelines for the future design and application of this novel molecular allotrope of carbon.     

石墨炔基本性能及其在放射化学领域的应用

石墨炔作为一种新型的二维碳材料，自2010年首次合成后即得到了广泛的关注和研究。目前石墨炔在储能、催化、电化学、医药和吸附等领域已经展现出广阔的应用前景。石墨炔具有特殊三角孔洞结构和大π键特性，对不同离子具有选择性吸附潜力，在放射化学领域有着潜在的应用价值。之前的工作表明，石墨炔在镧锕分离、钍铀分离、锶铯分离中具有显著的效果。与此同时，锕系离子被石墨炔吸附后呈现单离子态。石墨炔的π体系与锕系单离子的5f电子之间发生强烈的键合作用。而5f电子的反馈作用对锕系离子的选择性分离至关重要。本文首先对石墨炔的合成、性质、应用进行简短的综述，进而对石墨炔在放射化学领域中的初步结果进行介绍，最后对石墨炔在放射化学领域的应用进行了展望。     

Kerr Nonlinearity in 2D Graphdiyne for Passive Photonic Diodes

Graphdiyne is a new carbon allotrope comprising sp‐ and sp²‐hybridized carbon atoms arranged in a 2D layered structure. In this contribution, 2D graphdiyne is demonstrated to exhibit a strong light–matter interaction with high stability to achieve a broadband Kerr nonlinear optical response, which is useful for nonreciprocal light propagation in passive photonic diodes. Furthermore, advantage of the unique Kerr nonlinearity of 2D graphdiyne is taken and a nonreciprocal light propagation device is proposed based on the novel similarity comparison method. Graphdiyne has demonstrated a large nonlinear refractive index in the order of ≈10^?5 cm² W^?1, comparing favorably to that of graphene. Based on the strong Kerr nonlinearity of 2D graphdiyne, a nonlinear photonic diode that breaks time‐reversal symmetry is demonstrated to realize the unidirectional excitation of Kerr nonlinearity, which can be regarded as a significant demonstration of a graphdiyne‐based prototypical application in nonlinear photonics and might suggest an important step toward versatile graphdiyne‐based advanced passive photonics devices in the future.     

Graphdiyne Derivative as Multifunctional Solid Additive in Binary Organic Solar Cells with 17.3% Efficiency and High Reproductivity

Morphology tuning of the blend film in organic solar cells (OSCs) is a key approach to improve device efficiencies. Among various strategies, solid additive is proposed as a simple and new way to enable morphology tuning. However, there exist few solid additives reported to meet such expectations. Herein, chlorine-functionalized graphdiyne (GCl) is successfully applied as a multifunctional solid additive to fine-tune the morphology and improve device efficiency as well as reproductivity for the first time. Compared with 15.6% efficiency for control devices, a record high efficiency of 17.3% with the certified one of 17.1% is obtained along with the simultaneous increase of short-circuit current (J_sc) and fill factor (FF), displaying the state-of-the-art binary organic solar cells at present. The redshift of the film absorption, enhanced crystallinity, prominent phase separation, improved mobility, and decreased charge recombination synergistically account for the increase of J_sc and FF after introducing GCl into the blend film. Moreover, the addition of GCl dramatically reduces batch-to-batch variations benefiting mass production owing to the nonvolatile property of GCl. All these results confirm the efficacy of GCl to enhance device performance, demonstrating a promising application of GCl as a multifunctional solid additive in the field of OSCs.     

Few‐Layer Graphdiyne Nanosheets Applied for Multiplexed Real‐Time DNA Detection

Despite recent progress in 2D nanomaterials‐based biosensing, it remains challenging to achieve sensitive and high selective detection. This study develops few‐layer graphdiyne (GD) nanosheets (NSs) that are used as novel sensing platforms for a variety of fluorophores real‐time detection of DNA with low background and high signal‐to‐noise ratio, which show a distinguished fluorescence quenching ability and different affinities toward single‐stranded DNA and double‐stranded DNA. Importantly, for the first time, a few‐layer GD NSs‐based multiplexed DNA sensor is developed.     

A Universal Strategy for Constructing Seamless Graphdiyne on Metal Oxides to Stabilize the Electrochemical Structure and Interface

The structural and interfacial stabilities of metal oxides (MOs) are key issues while facing the volumetric variation and intensive interfacial polarization in electrochemical applications, including lithium‐ion batteries (LIBs), supercapacitors, and catalysts. The growth of a seamless all‐carbon interfacial layer on MOs with complex dimensions is not only a scientific problem, but also a practical challenge in these fields. Here, the growth of graphdiyne under ultramild condition is successfully implemented in situ for coating MOs of complex dimensions. The seamless all‐carbon interface and conductive network are formed at the same time. This method cleverly avoids the structural degradation of MOs at a high temperature in the presence of traditional carbon materials. Under the protection of the high‐quality graphdiyne layer, the samples as LIB anodes deliver high performances in terms of Coulomb efficiency, capacity, long‐term retention, and structural and interfacial stabilities. Both experimental achievements and theoretical calculations demonstrate that the graphdiyne is a particular protection layer for MOs and plays a crucial role for preventing the structural and interfacial degradation of the electrode. Furthermore, the universality of this method will promote the potential applications of many promising MOs in other electrochemical fields.