Zicheng Zuo

A Multianalyte Chemosensor on a Single Molecule: Promising Structure for an Integrated Logic Gate

A novel fluorescent probe that possess both BODIPY and Rhodamine moieties has been designed for the selective detection of Hg(2+) and Ba(2+) ions on the controlling by a logic gate. The characteristic fluorescence of the Ba(2+)-selective OFF-ON and the Hg(2+)-selective fluorescence bathochromic shift can be observed, and the concept has been used to construct a combinational logic circuit at the molecular level. These results will be useful for further molecular design to mimic the function of the complex logic gates on controlling.

Light Harvesting and Efficient Energy Transfer in Dendritic Systems: New Strategy for Functionalized Near‐Infrared BF2‐Azadipyrromethenes

A series of dendritic systems, which are capable of funneling energy from the periphery to the core, have been synthesized. The photophysical properties of the dendrimers, generations 0-2, have been determined. The light-harvesting ability of these compounds increases with increasing generation arising from the increase in molar extinction coefficient. Selective excitation of the donor leads to an efficient energy transfer (>90 %) to the acceptor. The approach provides a facile synthesis for modification of near-infrared BF2-Azadipyrromethene.

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.

Graphdiyne‐Supported NiCo2S4 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.

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.

Anchoring zero valence single atoms of nickel and iron on graphdiyne for hydrogen evolution

Electrocatalysis by atomic catalysts is a major focus of chemical and energy conversion effort. Although transition-metal-based bulk electrocatalysts for electrochemical application on energy conversion processes have been reported frequently, anchoring the stable transition-metal atoms (e.g. nickel and iron) still remains a practical challenge. Here we report a strategy for fabrication of ACs comprising only isolated nickel/iron atoms anchored on graphdiyne. Our findings identify the very narrow size distributions of both nickel (1.23 Å) and iron (1.02 Å), typical sizes of single-atom nickel and iron. The precision of this method motivates us to develop a general approach in the field of single-atom transition-metal catalysis. Such atomic catalysts have high catalytic activity and stability for hydrogen evolution reactions.Single atom catalysts provide the most efficient metal atoms usage and afford active site homogeneity, but surface attachment has proven challenging. Here, the authors use triple-bond-rich graphdiyne to anchor nickel/iron atoms and show high hydrogen evolution electrocatalysis activities.

Controllable growth of one-dimensional chiral nanostructures from an achiral molecule.

One achiral molecule of thioxanthone-anthracene (TX-A) is able to self-assemble into chiral nanowires by tuning the solvent with different polarity. Left- and right-handed nanowires with helix structure can be produced from chloroform and acetic ester solution of TX-A respectively. The SEM and TEM images confirm the formation of the helical nanowires. The results indicate that the solvent polarity has great influence in controlling of the self-assembly of organic molecules. The growth process demonstrates a promising pathway to investigate the self-assembling from achiral organic molecules to chiral aggregations.

Low-Temperature Growth of All-Carbon Graphdiyne on a Silicon Anode for High-Performance Lithium-Ion Batteries

In situ weaving an all-carbon graphdiyne coat on a silicon anode is scalably realized under ultralow temperature (25 °C). This economical strategy not only constructs 3D all-carbon mechanical and conductive networks with reasonable voids for the silicon anode at one time but also simultaneously forms a robust interfacial contact among the electrode components. The intractable problems of the disintegrations in the mechanical and conductive networks and the interfacial contact caused by repeated volume variations during cycling are effectively restrained. The as-prepared electrode demostrates the advantages of silicon regarding capacity (4122 mA h g-1 at 0.2 A g-1 ) with robust capacity retention (1503 mA h g-1 ) after 1450 cycles at 2 A g-1 , and a commercial-level areal capacity up to 4.72 mA h cm-2 can be readily approached. Furthermore, this method shows great promises in solving the key problems in other high-energy-density anodes.

Interfacial Synthesis of Conjugated Two-Dimensional N-Graphdiyne

We explored the interfacial synthesis of 2D N-graphdiyne films at the gas/liquid and liquid/liquid interfaces. Triazine- or pyrazine-based monomers containing ethynyl group were polymerized through the Glaser coupling reactions at interfaces. Several layered, highly ordered and conjugated 2D N-graphdiyne were obtained. Their structures were characterized by TEM, SEM, AFM, XPS, and Raman spectra. Thin films with minimum thickness of 4 nm could be prepared.

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.