An Electro-Optical Kerr Device Based on 2D Boron Nitride Liquid Crystals for Solar-Blind Communications.

Achieving light modulation in the spectral range of 200-280 nm is a prerequisite for solar-blind ultraviolet communication, where current technologies are mainly based on the electro-luminescent self-modulation of the ultraviolet source. External light modulation through the electro-birefringence control of liquid crystal (LC) devices has shown success in the visible-to-infrared regions. However, the poor stability of conventional LCs against ultraviolet irradiation and their weak electro-optical response make it challenging to modulate ultraviolet light. Here, an external ultraviolet light modulator is demonstrated using two-dimensional boron nitride LC. It exhibits robust ultraviolet stability and a record-high specific electro-optical Kerr coefficient of 5.1 × 10⁻2 m V-2, being three orders of magnitude higher than those of other known electro-optical media that are transparent (or potentially transparent) in the ultraviolent spectral range. The sensitive response enables fabricating transmissive and stable ultraviolet-C electro-optical Kerr modulators for solar-blind ultraviolet light. An M-ary coding array with high transmission density is also demonstrated for solar-blind ultraviolet communication.

An extended substrate screening strategy enabling a low lattice mismatch for highly reversible zinc anodes.

Aqueous zinc batteries possess intrinsic safety and cost-effectiveness, but dendrite growth and side reactions of zinc anodes hinder their practical application. Here, we propose the extended substrate screening strategy for stabilizing zinc anodes and verify its availability (dsubstrate: dZn(002) = 1: 1→dsubstrate: dZn(002)=n:1, n = 1, 2). From a series of calculated phyllosilicates satisfying dsubstrate ≈ 2dZn(002), we select vermiculite, which has the lowest lattice mismatch (0.38%) reported so far, as the model to confirm the effectiveness of "2dZn(002)" substrates for zinc anodes protection. Then, we develop a monolayer porous vermiculite through a large-scale and green preparation as a functional coating for zinc electrodes. Unique "planting Zn(002) seeds" mechanism for "2dZn(002)" substrates is revealed to induce the oriented growth of zinc deposits. Additionally, the coating effectively inhibits side reactions and promotes zinc ion transport. Consequently, the modified symmetric cells operate stably for over 300 h at a high current density of 50 mA cm-2. This work extends the substrate screening strategy and advances the understanding of zinc nucleation mechanism, paving the way for realizing high-rate and stable zinc-metal batteries.

Scalable Production of 2D Minerals by Polymer Intercalation and Adhesion for Multifunctional Applications.

Natural and sustainable 2D minerals have many unique properties and may reduce reliance on petroleum-based products. However, the large-scale production of 2D minerals remains challenging. Herein, a green, scalable, and universal polymer intercalation and adhesion exfoliation (PIAE) method to produce 2D minerals such as vermiculite, mica, nontronite, and montmorillonite with large lateral sizes and high efficiency, is developed. The exfoliation relies on the dual functions of polymers involving intercalation and adhesion to expand interlayer space and weaken interlayer interactions of minerals, facilitating their exfoliation. Taking vermiculite as an example, the PIAE produces 2D vermiculite with an average lateral size of 1.83 ± 0.48 µm and thickness of 2.40 ± 0.77 nm at a yield of ≈30.8%, surpassing state-of-the-art methods in preparing 2D minerals. Flexible films are directly fabricated by the 2D vermiculite/polymer dispersion, exhibiting outstanding performances including mechanical strength, thermal resistance, ultraviolet shielding, and recyclability. The representative application of colorful multifunctional window coatings in sustainable buildings is demonstrated, indicating the potential of massively produced 2D minerals.

A Polarized Gel Electrolyte for Wide-Temperature Flexible Zinc-Air Batteries.

The development of flexible zinc-air batteries (FZABs) has attracted broad attention in the field of wearable electronic devices. Gel electrolyte is one of the most important components in FZABs, which is urgent to be optimized to match with Zn anode and adapt to severe climates. In this work, a polarized gel electrolyte of polyacrylamide-sodium citric (PAM-SC) is designed for FZABs, in which the SC molecules contain large amount of polarized -COO- functional groups. The polarized -COO- groups can form an electrical field between gel electrolyte and Zn anode to suppress Zn dendrite growth. Besides, the -COO- groups in PAM-SC can fix H2 O molecules, which prevents water from freezing and evaporating. The polarized PAM-SC hydrogel delivers a high ionic conductivity of 324.68 mS cm-1 and water retention of 96.85 % after being exposed for 96 h. FZABs with the PAM-SC gel electrolyte exhibit long cycling life of 700 cycles at -40 °C, showing the application prospect under extreme conditions.

Deep ultraviolet hydrogel based on 2D cobalt-doped titanate.

Birefringent optical elements that work in deep ultraviolet (DUV) region become increasingly important these years. However, most of the DUV optical elements have fixed birefringence which is hard to be tuned. Here, we invent a birefringence-tunable optical hydrogel with mechano-birefringence effect in the DUV region, based on two-dimensional (2D) low-cobalt-doped titanate. This 2D oxide material has an optical anisotropy factor of 1.5 × 10-11 C2 J-1 m-1, larger than maximum value obtained previously, leading to an extremely large specific magneto-optical Cotton-Mouton coefficient of 3.9 × 106 T-2 m-1. The extremely large coefficient enables the fabrication of birefringent hydrogel in a small magnetic field with an ultra-low concentration of 2D oxide material. The hydrogel can stably and continuously modulate 303 nm DUV light with large phase tunability by varying the strain (compression or stretching) from 0 to 50%. Our work opens the door to design and fabricate new proof-of-concept DUV birefringence-tunable element, as demonstrated by optical hydrogels capable of DUV modulation by mechanical stimuli.

Isolating Contiguous Fe Atoms by Forming a Co-Fe Intermetallic Catalyst from Spent Lithium-Ion Batteries to Regulate Activity for Zinc-Air Batteries.

The recycling of spent lithium-ion batteries (LIBs) has become a necessity for recovering valuable resources and protecting the environment to support sustainable development. We report the design of a highly efficient CoFe/C catalyst by combining the Co and Fe wastes from spent LIBs with sawdust-derived carbon, which were cathode materials in zinc-air batteries (ZABs). As a result of the electrostatic attraction between the Co3+/Fe3+ cations and the hydroxyl groups in sawdust, CoFe nanoparticles are uniformly dispersed in the CoFe/C catalyst after annealing. The Fe atoms in the CoFe nanoparticles are all isolated into single sites by the Co atoms, which redistribute the electrons in the CoFe/C catalyst. The catalyst produced a Pt-like dissociative mechanism, contributing to an excellent oxygen reduction reaction performance. After assembly in ZABs, the CoFe/C catalyst cathode exhibits a long cycling stability of 350 h and an impressive power density of 199.2 mW cm-2. The CoFe/C catalyst cathode has also been used in flexible ZABs to power LEDs or charge a mobile phone. The work combines spent LIBs with sawdust to fabricate high-performance catalysts, which could reduce environmental pollution and realize high economic value.

Recycling spent LiNi1-x-yMnxCoyO2 cathodes to bifunctional NiMnCo catalysts for zinc-air batteries.

SignificanceIn recent years, lithium-ion batteries (LIBs) have been widely applied in electric vehicles as energy storage devices. However, it is a great challenge to deal with the large number of spent LIBs. In this work, we employ a rapid thermal radiation method to convert the spent LIBs into highly efficient bifunctional NiMnCo-activated carbon (NiMnCo-AC) catalysts for zinc-air batteries (ZABs). The obtained NiMnCo-AC catalyst shows excellent electrochemical performance in ZABs due to the unique core-shell structure, with face-centered cubic Ni in the core and spinel NiMnCoO4 in the shell. This work provides an economical and environment-friendly approach to recycling the spent LIBs and converting them into novel energy storage devices.

A 2D material-based transparent hydrogel with engineerable interference colours.

Transparent hydrogels are key materials for many applications, such as contact lens, imperceptible soft robotics and invisible wearable devices. Introducing large and engineerable optical anisotropy offers great prospect for endowing them with extra birefringence-based functions and exploiting their applications in see-through flexible polarization optics. However, existing transparent hydrogels suffer from limitation of low and/or non-fine engineerable birefringence. Here, we invent a transparent magneto-birefringence hydrogel with large and finely engineerable optical anisotropy. The large optical anisotropy factor of the embedded magnetic two-dimensional material gives rise to the large magneto-birefringence of the hydrogel in the transparent condition of ultra-low concentration, which is several orders of magnitude larger than usual transparent magnetic hydrogels. High transparency, large and tunable optical anisotropy cooperatively permit the magnetic patterning of interference colours in the hydrogel. The hydrogel also shows mechanochromic and thermochromic property. Our finding provides an entry point for applying hydrogel in optical anisotropy and colour centred fields, with several proof-of-concept applications been demonstrated.

2D Functional Minerals as Sustainable Materials for Magneto-Optics.

Liquid crystal devices using organic molecules are nowadays widely used to modulate transmitted light, but this technology still suffers from relatively weak response, high cost, toxicity and environmental concerns, and cannot fully meet the demand of future sustainable society. Here, an alternative approach to color-tunable optical devices, which is based on sustainable inorganic liquid crystals derived from 2D mineral materials abundant in nature, is described. The prototypical 2D mineral of vermiculite is massively produced by a green method, possessing size-to-thickness aspect ratios of >103 , in-plane magnetization of >10 emu g-1 , and an optical bandgap of >3 eV. These characteristics endow 2D vermiculite with sensitive magneto-birefringence response, been several orders of magnitude larger than organic counterparts, as well as capability of broad-spectrum modulation. The finding consequently permits the fabrication of various magnetochromic or mechanochromic devices with low or even zero-energy consumption during operation. This work creates opportunities for the application of sustainable materials in advanced optics.

Jahn-Teller Distortion Induced Mn2+-Rich Cathode Enables Optimal Flexible Aqueous High-Voltage Zn-Mn Batteries.

Although one of the most promising aqueous batteries, all Zn-Mn systems suffer from Zn dendrites and the low-capacity Mn4+/Mn3+ process (readily leading to the occurrence of Jahn-Teller distortion, which in turn causes structural collapse and voltage/capacity fading). Here, the Mn3+ reconstruction and disproportionation are exploited to prepare the stable, Mn2+-rich manganese oxides on carbon-cloth (CMOs) in a discharged state through an inverted design, which promotes reversible Mn2+/Mn4+ kinetics and mitigates oxygen-related redox activity. Such a 1.65 V Mn2+-rich cathode enable constructing a 2.2 V Zn-Mn battery, providing a high area capacity of 4.16 mA h cm-2 (25 mA h cm-2 for 10 mL electrolyte) and superior 4000-cycle stability. Moreover, a flexible hybrid 2.7 V Zn-Mn battery is constructed using 2-pH hydrogel electrolytes to demonstrate excellent practicality and stability. A further insight has been gained to the commercial application of aqueous energy storage devices toward low-cost, high safety, and excellent energy density.

Enantioselective synthesis of polycyclic pyrrole derivatives by iridium-catalyzed asymmetric allylic dearomatization and ring-expansive migration reactions.

Herein, we report an N-alkylation of pyrroles triggered by an unprecedented selective ring-expansive migration of the spiro-2H-pyrrole intermediates obtained via Ir-catalyzed asymmetric allylic dearomatization. The reaction affords a series of tetrahydropyrrolo[1,2-c]pyrimidine derivatives in good yields (up to 88%) with excellent enantioselectivity (up to >99% ee). The proposed reaction mechanism is supported by DFT calculations and the characterization of the key intermediate.

Study on the influence of carbon emission constraints on the performance of thermal power enterprises.

With the increase of carbon dioxide concentration in the atmosphere, the living environment of human beings is seriously affected. As a high carbon emission industry in China, thermal power enterprises are the key areas of carbon emission reduction in China. This paper first uses Super-SBM model to measure the performance of China's 18 major thermal power enterprises in 2009-2018 from a static point of view. After considering the carbon emission constraints, it analyzes the degree of change in enterprise performance, and finds that the impact of carbon emission constraints on enterprise performance is not absolute. After that, with the help of Malmquist index model, this paper discusses the dynamic changes of thermal power enterprises' performance under carbon emission constraint in recent 10 yrs. The results show that the overall performance of carbon emission constraint is in a weak regression stage and summarizes the disadvantages of different enterprises. On the basis of the research conclusion, this paper puts forward countermeasures and suggestions to further improve the performance of Chinese thermal power enterprises under the carbon emission constraints in the future, which is conducive to different enterprises to optimize their own disadvantages.

Recyclable and tear-resistant all-in-one supercapacitor with dynamic electrode/electrolyte interface.

All-in-one supercapacitors constitute an indispensable part in adapting to the rapid development of flexible energy storage equipment. Herein, an all-in-one configured PANI supercapacitor with a dynamic electrode/electrolyte interface was designed through hydrogen bonds and metal coordination bonds. The supercapacitor exhibits remarkable electrochemical capacitance (162 F g-1 at 0.5 A g-1, 137.4 mF cm-2 at 0.5 A cm-2) and excellent structural stabilities (almost no degradation in performance and structural damage in the cases of bending, folding, stretching and self-healing process). Besides, the hydrogel electrode can be efficiently recycled through a convenient method without virtual loss of electrochemical performance. Construction of the dynamic interface inside the supercapacitor provides a practical guidance for large-scale preparation of flexible energy storage devices, electronic skin and stretchable sensors.

Palladium(0)-Catalyzed Intermolecular Asymmetric Allylic Dearomatization of Polycyclic Indoles.

An intermolecular Pd-catalyzed allylic dearomatization reaction of polycyclic indoles with substituted allylic carbonates was realized in the presence of a newly synthesized chiral phosphoramidite ligand. Various polycyclic indoline and indolenine derivatives were successfully synthesized in excellent yields (up to 99%) with excellent enantioselectivity (up to 98% ee). The obtained products could undergo versatile transformations, increasing the application potential of the method in organic synthesis.

Synthesis of C3-Methyl-Substituted Pyrroloindolines and Furoindolines via Cascade Dearomatization of Indole Derivatives with Methyl Iodide.

A highly efficient method for constructing C3-methyl-substituted pyrroloindolines and furoindolines via cascade dearomatization reaction of indole derivatives with methyl iodide was developed. This protocol offers a direct approach to a wide range of C3 methyl substituted pyrroloindolines under mild conditions. The utility of this method was further demonstrated in the concise synthesis of (±)-esermethol.

Iridium-Catalyzed Enantioselective Synthesis of Pyrrole-Annulated Medium-Sized-Ring Compounds.

Enantioselective synthesis of pyrrole-annulated medium-sized-ring compounds by an iridium-catalyzed allylic dearomatization/retro-Mannich/hydrolysis sequence is presented. Various substituted pyrrole-annulated seven- and eight-membered-ring products were obtained under mild reaction conditions with moderate to good yields and excellent enantioselectivity. Additionally, these products contain a scaffold widely distributed in natural products and biologically active compounds. The current method provides a convenient way for accessing such pyrrole-anuulated medium-sized-ring compounds.

Pd-catalyzed cascade allylic alkylation and dearomatization reactions of indoles with vinyloxirane.

We have developed Pd-catalyzed intermolecular Friedel-Crafts-type allylic alkylation and allylic dearomatization reactions of substituted indoles bearing a nucleophilic group with vinyloxirane, providing an efficient method to synthesize structurally diverse tetrahydrocarboline and spiroindolenine derivatives under mild conditions.

Palladium(0)-Catalyzed Intermolecular Allylic Dearomatization of Indoles by a Formal [4+2] Cycloaddition Reaction.

Bridged indoline derivatives were synthesized by an intermolecular Pd-catalyzed allylic dearomatization reaction of substituted indoles. The reaction between indoles and allyl carbonates bearing a nucleophilic alcohol side-chain proceeds in a cascade fashion, providing bridged indolines in excellent enantioselectivity.

Relativistic reverberation in the accretion flow of a tidal disruption event.

Our current understanding of the curved space-time around supermassive black holes is based on actively accreting black holes, which make up only ten per cent or less of the overall population. X-ray observations of that small fraction reveal strong gravitational redshifts that indicate that many of these black holes are rapidly rotating; however, selection biases suggest that these results are not necessarily reflective of the majority of black holes in the Universe. Tidal disruption events, where a star orbiting an otherwise dormant black hole gets tidally shredded and accreted onto the black hole, can provide a short, unbiased glimpse at the space-time around the other ninety per cent of black holes. Observations of tidal disruptions have hitherto revealed the formation of an accretion disk and the onset of an accretion-powered jet, but have failed to reveal emission from the inner accretion flow, which enables the measurement of black hole spin. Here we report observations of reverberation arising from gravitationally redshifted iron Kα photons reflected off the inner accretion flow in the tidal disruption event Swift J1644+57. From the reverberation timescale, we estimate the mass of the black hole to be a few million solar masses, suggesting an accretion rate of 100 times the Eddington limit or more. The detection of reverberation from the relativistic depths of this rare super-Eddington event demonstrates that the X-rays do not arise from the relativistically moving regions of a jet, as previously thought.

An Iridium(I) N-Heterocyclic Carbene Complex Catalyzes Asymmetric Intramolecular Allylic Amination Reactions.

A chiral iridium(I) N-heterocyclic carbene complex was reported for the first time as the catalyst in the highly enantioselective intramolecular allylic amination reaction. The current method provides facile access to biologically important enantioenriched indolopiperazinones and piperazinones in good yields (74-91 %) and excellent enantioselectivities (92-99 % ee). Preliminary mechanistic investigations reveal that the C-H activation occurs at the position ortho to the N-aryl group of the ligand.