Direct solar energy conversion on zinc-air battery.

A concept of solar energy convertible zinc-air battery (SZAB) is demonstrated through rational design of an electrode coupled with multifunction. The multifunctional electrode is fabricated using nitrogen-substituted graphdiyne (N-GDY) with large π-conjugated carbonous network, which can work as photoresponsive bifunctional electrocatalyst, enabling a sunlight-promoted process through efficient injection of photoelectrons into the conduction band of N-GDY. SZAB enables direct conversion and storage of solar energy during the charging process. Such a battery exhibits a lowered charge voltage under illumination, corresponding to a high energy efficiency of 90.4% and electric energy saving of 30.3%. The battery can display a power conversion efficiency as high as 1.02%. Density functional theory calculations reveal that the photopromoted oxygen evolution reaction kinetics originates from the transition from the alkyne bonds to double bonds caused by the transfer of excited electrons, which changes the position of highest occupied molecular orbital and lowest unoccupied molecular orbital, thus greatly promoting the formation of intermediates to the conversion process. Our findings provide conceptual and experimental confirmation that batteries are charged directly from solar energy without the external solar cells, providing a way to manufacture future energy devices.

The Alkynyl π Bond of sp-C Enhanced Rapid, Reversible Li-C Coupling to Accelerate Reaction Kinetics of Lithium Ions.

Graphdiyne (GDY) is a promising anode for rechargeable batteries with high capacity, outstanding cyclic stability, and low diffusion energy. The unique structure of GDY endows distinctive mechanisms for metal-ion storage, and it is of great significance to further visualize the complex reaction kinetics of the redox process. Here, we systematically tracked the reaction kinetics and provided mechanistic insights into the lithium ions in the GDY to reveal the feature of the cation-π effect. It has been demonstrated that, unlike only one π bond in sp2-C, π electrons provided by one of the two alkynyl π bonds in sp-C can achieve proper interaction and speedy capture of lithium ions; thus, reversible Li-C coupling can be formed between electron-rich sp-C and lithium ions. In addition to interlayer intercalation in sp2-C regions, nanopores filling triangular-like cavities composed of highly conjugated sp-C contribute to the major capacity in flat voltage plateau regions. Therefore, a capture/pores filling-intercalation hybrid mechanism can be found in GDY. The coexistence of sp and sp2 carbon enables GDY electrodes with rapid Li+ diffusion, high capacity of over 1435 mAh g-1, extraordinary rate capability, and cyclic stability for more than 10000 cycles at 10A g-1. These results provide guidance for developing advanced carbon electrodes with optimized reaction kinetics for rechargeable batteries.

Directly Growing Graphdiyne Nanoarray Cathode to Integrate an Intelligent Solid Mg-Moisture Battery.

A continuous humidity and solar-light dual responsive intelligent solid Mg-moisture battery (SMB) with a graphdiyne nanosheets array was fabricated. The integrated battery works based on a new concept of chemical bond conversion on the surface of the graphdiyne nanosheets array that is grown in situ on a 3D melamine sponge (GDY/MS). The unique structure, excellent catalytic, and semiconductor performance of GDY endows the GDY/MS with some outstanding characteristics on trapping and transferring water molecules, catalyzing HER, and utilizing solar energy, making the GDY/MS a new generation cathode for a high-performance intelligent SMB. The performance of the GDY/MS-based smart SMB (GSMB) can be continuously tuned by humidity and solar-light. The GSMB shows a significant positive correlation between open circuit potential (OCP) and humidity, while the natural band gap of GDY makes it further act as a photoelectrode to capture light and generate photoelectrons. The GSMB can be applied as a self-power humidity monitor with an ultrafast response time of <0.24 s, a recovery time of <0.16 s, and a sensitive (36,600%) respiratory sensing performance. This simple and efficient battery-made strategy represents the future development direction of self-power supply equipment, intelligent electronic devices, and intelligent battery integration.

Boosting Fe Cationic Vacancies with Graphdiyne to Enhance Exceptional Pseudocapacitive Lithium Intercalation.

Modulating the electronic structure of electrode materials at atomic level is the key to controlling electrodes with outstanding rate capability. On the basis of modulating the iron cationic vacancies (IV) and electronic structure of materials, we proposed the method of preparing graphdiyne/ferroferric oxide heterostructure (IV-GDY-FO) as anode materials. The goal is to motivate lithium-ion batteries (LIBs) toward ultra-high capacity, superior cyclic stability, and excellent rate performance. The graphdiyne is used as carriers to disperse Fe3 O4 uniformly without agglomeration and induce high valence of Fe with reducing the energy in the system. The presence of Fe vacancy could regulate the charge distribution around vacancies and adjacent atoms, leading to facilitate electronic transportation, enlarge the lithium-ion diffusion, and decrease Li+ diffusion barriers, and thus displaying significant pseudocapacitive process and advantageous lithium-ion storage. The optimized electrode IV-GDY-FO reveals a capacity of 2084.1 mAh g-1 at 0.1 C, superior cycle stability and rate performance with a high specific capacity of 1057.4 mAh g-1 even at 10 C.

Development of Fluorogenic Probes for Rapid High-Contrast Imaging of Transient Nuclear Localization of Sirtuin†3.

Protein labeling using fluorogenic probes enables the facile visualization of proteins of interest. Herein, we report new fluorogenic probes consisting of a rationally designed coumarin ligand for the live-cell fluorogenic labeling of the photoactive yellow protein (PYP)-tag. On the basis of the photochemical mechanisms of coumarin and the probe-tag interactions, we introduced a hydroxy group into an environment-sensitive coumarin ligand to modulate its spectroscopic properties and increase the labeling reaction rate. The resulting probe had a higher labeling reaction rate constant and a greater fluorescence OFF-ON ratio than any previously developed PYP-tag labeling probe. The probe enabled the fluorogenic labeling of intracellular proteins within minutes. Furthermore, we used our probe to investigate the localization of sirtuin 3 (SIRT3), a mitochondrial deacetylase. Although the nuclear localization of SIRT3 has been controversial, this transient nuclear localization was clearly captured by the rapid, high-contrast imaging enabled by our probe.

Live-Cell Imaging of Protein Degradation Utilizing Designed Protein-Tag Mutant and Fluorescent Probe with Turn-Off Switch.

Protein degradation plays various roles in cellular homeostasis and signal transduction. Real-time monitoring of the degradation process not only contributes to the elucidation of relevant biological phenomena but also offers a powerful tool for drug discoveries targeting protein degradation. Fluorescent protein labeling with a protein tag and a synthetic fluorescent probe is a powerful technique that enables the direct visualization of proteins of interest in living cells. Although a variety of protein tags and their labeling probes have been reported, techniques for the visualization of protein degradation in living cells remain limited. In order to overcome this limitation, we herein employed a PYP-tag labeling probe with a fluorescence turn-off switch that enables the imaging of protein degradation. Furthermore, we performed a structure-based design of a PYP-tag to stabilize a complex formed by the probe and the protein tag for long-term live-cell imaging. We successfully applied this technique to live-cell imaging of the degradation process of Regnase-1 in response to immunostimulation.

Advanced Multilayered Electrode with Planar Building Blocks Structure for High-Performance Lithium-Ion Storage.

To achieve the high-performance of lithium-ion battery, the optimization of electrode materials has generally been considered as the one of the important methods. But most of those works pay attention to the new materials preparation or interface modification rather than the structural innovation. Here, an advanced electrode (GDY/BP/GDY-E) with multilevel layered architecture constructed by planar building blocks stacking structure has been designed and fabricated to explore the structure design of the electrode. This new structure is assembled by graphdiyne (GDY) and black phosphorus (BP) in parallel to form a building block (GDY/BP/GDY). The electric fields between the two GDY sides of the planar building block structure contribute to the superior migration dynamics of lithium ions and desirable pseudocapacitance behavior. Meanwhile, the planar stacking structure of GDY/BP/GDY can efficiently inhibit volume expansion of BP and a series of parasitic reactions of electrolytes during the long-term cycling. The advanced GDY/BP/GDY-E exhibits excellent high-rate performance (1418.8 mAh g-1 at 0.1 A g-1 ) and cycling stability (391.7 mAh g-1 after 5000 cycles at 10 A g-1 ). Such structural design of electrode materials shows a new way to develop high-performance electrodes.

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.

In Situ Coating Graphdiyne for High-Energy-Density and Stable Organic Cathodes.

The preparation of organic small-molecule cathodes is simple and low-cost; however, their low conductivity and molecular dissolution are two key issues that mean their energy density and power performance are far lower than those of inorganic batteries, thus hindering their practical application. To develop an effective coating technology is the key to obtain high-performance organic batteries. A general method of in situ weaving all-carbon graphdiyne nanocoatings is demonstrated. The graphdiyne can be conformally weaved on organic particles under mild conditions so that the conductivity is increased and the dissolution is suppressed. After weaving graphdiyne nanocoat, the active mass of the small-molecule organic cathodes rise to 93%, thus delivering a higher energy density of 310 W h kg-1 than previously reported, and the power performance and long-term stability are greatly improved. Additionally, this method shows great potential to become the crucial technology for fabricating organic batteries with energy density close to prevailing lithium-ion batteries.

High-Performance Cathode of Sodium-Ion Batteries Enabled by a Potassium-Containing Framework of K0.5Mn0.7Fe0.2Ti0.1O2.

Sodium-ion batteries (SIBs) are promising candidates for large-scale electric energy storage with abundant sodium resources. However, their development is challenged by the availability of satisfactory cathode materials with stable framework to accommodate the transportation of large-sized Na+ (1.02 Å), whose continuous insertion/extraction can easily cause irreversible volumetric deformation in the crystalline material, leading to inevitable structural failure and capacity fading. Here, different from the previous synthesis efforts targeting at Na+ containing compounds, we unveil the possibility of achieving a highly reversible sodiation/desodiation process by resorting to a K+-based layered metal oxide formulated as K0.5Mn0.7Fe0.2Ti0.1O2 (KMFT), which is a P2 type in structure with a wide interlayer spacing to sit K+ (1.38 Å). We demonstrate that an initial K+/Na+ exchange can introduce Na+ into the lattice while a small amount of K+ remains inside, which plays a significant role in ensuring enlarged channels for a fast and stable Na+ diffusion. The KMFT electrode delivers a high initial discharge capacity of 147.1 mA h g-1 at 10 mA g-1 and outstanding long cycling stability with capacity retention of 71.5% after 1000 cycles at 500 mA g-1. These results provide a new design strategy for the development of stable SIBs cathodes to facilitate their future applications.

Pitch-Derived Soft Carbon as Stable Anode Material for Potassium Ion Batteries.

Potassium ion batteries (KIBs) have emerged as a promising energy storage system, but the stability and high rate capability of their electrode materials, particularly carbon as the most investigated anode ones, become a primary challenge. Here, it is identified that pitch-derived soft carbon, a nongraphitic carbonaceous species which is paid less attention in the battery field, holds special advantage in KIB anodes. The structural flexibility of soft carbon makes it convenient to tune its crystallization degree, thereby modulating the storage behavior of large-sized K+ in the turbostratic carbon lattices to satisfy the need in structural resilience, low-voltage feature, and high transportation kinetics. It is confirmed that a simple thermal control can produce structurally optimized soft carbon that has much better battery performance than its widely reported carbon counterparts such as graphite and hard carbon. The findings highlight the potential of soft carbon as an interesting category suitable for high-performance KIB electrode and provide insights for understanding the complicated K+ storage mechanisms in KIBs.