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Abstract Developing mild photocatalytic bromination strategies using sustainable bromo source has been attracting intense interests, but there is still much room for improvement. Full utilization of redox centers of photocatalysts for efficient generation of Br+ species is the key. Herein we report heterogenous organophotocatalytic HBr oxidation coupled with oxygen reduction to furnish Br2 and H2O2 for effective bromination of arenes over Al2O3 supported perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA). Mechanism studies suggest that O-vacancy in Al2O3 can provide Lewis-acid-type anchoring sites for O2, enabling unexpected dual-electron transfer from anchored photoexcited PTCDA to chemically bound O2 to produce H2O2. The in-situ generated H2O2 and Br2 over redox centers work together to generate HBrO for bromination of arenes. This work provides new insights that heterogenization of organophotocatalysts can not only help to improve their stability and recyclability, but also endow them with the ability to trigger unusual reaction mode via cooperative catalysis with supports.

Abstract In this work, via engineering the conformation of cobalt active center in cobalt phthalocyanine molecular catalyst, the catalytic efficiency of electrochemical carbon monoxide reduction to methanol can be dramatically tuned. Based on a collection of experimental investigations and density functional theory calculations, it reveals that the electron rearrangement of the Co 3d orbitals of cobalt phthalocyanine from the low-spin state (S = 1/2) to the high-spin state (S = 3/2), induced by molecular conformation change, is responsible for the greatly enhanced CO reduction reaction performance. Operando attenuated total reflectance surface-enhanced infrared absorption spectroscopy measurements disclose accelerated hydrogenation of CORR intermediates, and kinetic isotope effect validates expedited proton-feeding rate over cobalt phthalocyanine with high-spin state. Further natural population analysis and density functional theory calculations demonstrate that the high spin Co2+ can enhance the electron backdonation via the d xz /d yz −2π* bond and weaken the C-O bonding in *CO, promoting hydrogenation of CORR intermediates.

Perylenetetracarboxylic dianhydride (PTCDA) derivatives have received significant attention as molecule photocatalysts. However, the poor recyclability of molecule-type photocatalysts hinders their widespread applications. Herein, immobilization of PTCDA on Al2O3 was achieved by simply physical mixing, which not only dramatically improved their recyclability, but also surprisingly improved the reactivity. A mechanism study suggested that the photo-exited state (PTCDA*) of PTCDA could promote the oxidation of thioanisole to generate PTCDA•−, which sequentially reduces oxygen to furnish superoxide radicals to achieve the catalytic cycle. Herein, the immobilization support Al2O3 was able to facilitate the strong adsorption of thioanisole, thereby boosting the photocatalytic activity. This work provides a new insight that the immobilization of organic molecular photocatalysts on those supports with proper adsorption sites could furnish highly efficient, stable, and recyclable molecular-based heterogeneous photocatalysts.

Abstract One of the most unique properties of two‐dimensional carbides and nitrides of transition metals (MXenes) is their excellent water dispersibility and yet possessing superior electrical conductivity but their industrial‐scale application is limited by their costly chemical synthesis methods. In this work, the niche feature of MXenes was capitalized in the packed‐bed electrochemical reactor to produce MXenes at an unprecedented reaction rate and yield with minimal chemical waste. A simple NH4F solution was employed as the green electrolyte, which could be used repeatedly without any loss in its efficacy. Surprisingly, both fluoride and ammonium were found to play critical roles in the electrochemical etching, functionalization, and expansion of the layered parent materials (MAXs) through which the liberation of ammonia gas was observed. The electrochemically produced MXenes with excellent conductivity, applied as supercapacitor electrodes, could deliver an ultrahigh volumetric capacity (1408 F cm−3) and a volumetric energy density (75.8 Wh L−1). This revolutionary green, energy‐efficient, and scalable electrochemical route will not only pave the way for industrial‐scale production of MXenes but also open up a myriad of versatile electrochemical modifications for improved functional MXenes.

Mixed dimensional 2D/3D halide perovskite solar cells practically deliver poorer efficiency, and the 2D fragments have been considered responsible. Here, the authors unveil a photoinduced carrier blocking effect at the 2D/3D perovskite interface that could truly jeopardize device parameters.

Abstract In this article, subleading (in 1/N) corrections to the action of the one loop dilatation operator in the su(3) sector of N $$ \mathcal{N} $$ = 4 super Yang-Mills theory are studied. We focus on the system of operators dual to two giant graviton systems, which have a bare dimension ∼ O $$ \mathcal{O} $$ (N) and are a linear combination of restricted Schur polynomials with p = 2 long columns. At the leading order the dilatation operator gives rise to the free part of an emergent Yang-Mills theory, arising from the open string excitations of the giant gravitons. We verify that the terms we study describe interactions between these open string excitations. The interactions have the U(1)×U(1) gauge invariance expected for a pair of separated branes.

All-organic perovskites exhibit structural tunability and solution-processability, but are disadvantaged by a lower coercive field compared to inorganic ones. Here, the authors demonstrate that modulating hydrogen bond strength in such perovskites can generate a large coercive field.

Precisely regulating Pt catalytic sites is important and challenging. Herein the authors engineer the clustering of single atomic Te vacancies in atomically thin PtTe2 to optimize the electronic structure, adsorption energy, and catalytic performance of atomically defined Pt sites.

Vortex beams with optical orbital angular momentum have broad prospects in future high-speed and large-capacity optical communication. In this investigation of materials science, we found that low-dimensional materials have feasibility and reliability in the development of optical logic gates in all-optical signal processing and computing technology. We found that spatial self-phase modulation patterns through the MoS2 dispersions can be modulated by the initial intensity, phase, and topological charge of a Gauss vortex superposition interference beam. We utilized these three degrees of freedom as the input signals of the optical logic gate, and the intensity of a selected checkpoint on spatial self-phase modulation patterns as the output signal. By setting appropriate thresholds as logic codes 0 and 1, two sets of novel optical logic gates, including AND, OR, and NOT gates, were implemented. These optical logic gates are expected to have great potential in optical logic operations, all-optical networks, and all-optical signal processing.

Controllable deuteration of N-alkyl amines is crucial in drug-development as they constitute over 50% of the top-selling drugs. Here, the authors report a polymeric semiconductor acting as photocatalyst in water-splitting and in isotope alkanol-oxidation by photoexcited electron-hole pairs, and furnishing deuterated amines.

The fabrication of singly dispersed metal cluster catalysts with atomic-level control of dopants is a long-standing challenge. Here, the authors report a strategy for the synthesis of a precisely doped single cluster catalyst which shows exceptional activity for electrochemical dinitrogen reduction.

Abstract 2D ferroelectricity in van‐der‐Waals‐stacked materials such as indium selenide (In2Se3) has attracted interests because the ferroelectricity is robust even in ultrathin layers, which is useful for the miniaturization of ferroelectric field effect transistors. To implement In2Se3 in nanoscale ferroelectric devices, an understanding of the domain structure and switching dynamics in the 2D limit is essential. In this study, a biased scanning tunnelling microscopy (STM) tip is used to locally switch polarized domains in β′‐In2Se3, and the reconfiguration of these domains are directly visualized using STM. The room‐temperature surface of β′‐In2Se3 breaks into 1D nanostriped domains, which changes into a zig‐zag striped domains of β″ phase at low temperatures. These two types of domains can coexist, and by applying a tip‐sample bias, they can be interchangeably switched locally, showing volatile or nonvolatile like behavior depending on the threshold voltage applied. An atomic model is proposed to explain the switching mechanism based on tip‐induced flexoelectric effect and the ferroelastic switching between β′ and β″ phases.

Abstract Two‐dimensional transition metal dichalcogenides (TMDs) play host to a wide range of novel topological states, such as quantum spin Hall insulators, superconductors, and Weyl semimetals. The rich polymorphism in TMDs suggests that phase engineering can be used to switch between different charge order states. Intercalation of atoms or molecules into the van der Waals gap of TMDs has emerged as a powerful approach to modify the properties of the material, leading to phase transition or the formation of substoichiometric phases via compositional tuning, thus broadening the electronic and optical landscape of these materials for a wide range of applications. Here, we review the current efforts in the preparation of intercalated TMD. The challenges and opportunities for intercalated TMDs to create a new device paradigm for material science are discussed.

Li metal batteries (LMBs) are known as the ideal energy storage candidates for the future rechargeable batteries due to the high energy density. However, uncontrolled Li dendrites growing during charge/discharge process causes extremely low coulombic efficiency and short lifespan. In this work, a thin lithiophilic layer of Ag was coated on the bare Li surface via a thermal evaporation method, which alleviated volume variations and suppressed Li dendrites growth during cycling. As a result, a long lifespan of 250 h at a current density of 1 mA cm−2 was achieved in the symmetric cell when using the Ag-modified Li foil (Ag@Li). The LiFePO4|Li full cell demonstrated an excellent cycling performance with a high specific capacity of 131 mAh g−1 even after 300 cycles at 0.5 C. This study offers a suitable method for stabilizing Li metal anodes in LMBs.

Controllable synthesis of single atom catalysts with sufficiently high metal loading remains challenging due to the tendency of agglomeration. Here the authors synthesize a series of stable atomically dispersed cobalt atoms on graphene with high Co loadings via the regeneration of active sites by atomic layer deposition.

Developing convenient deuterium labeling procedures is important in organic synthesis and the pharmaceutical industry. Here, the authors report a mild photocatalytic strategy for controllable deuteration of halides using D2O as the reagent and porous CdSe nanosheets as the catalyst.

Beams carrying orbital angular momentum (OAM) are very helpful in enhancing the information carrying capacity in free-space optical communications. However, atmospheric turbulence and energy attenuation will seriously affect communication quality and signal transmissions. Here, a novel coherent separation detection technology for OAM mode division multiplexing is proposed, and numerical simulation work is conducted. With the proposed structure, two light beams with different OAM states, each encoded with 16-quadrature-amplitude modulation orthogonal frequency-modulated (QAM-OFDM) signals, can be demultiplexed and allow two orders of magnitude bit error rate (BER) lower than direct separation detection. Moreover, we show the scalability of multiplexing four OAM beams, achieving a 20 m free-space transmission with BER below 3.8 × 10–3 for all channels at signal-noise ratio (SNR) 18 dB. Our results show that coherent separation detection has excellent antinoise performance and can effectively extend the communication distance. It also paves the way for entirely new coherent optical OAM communications.

The functional groups of organic gas-sensing materials play a crucial role in adsorbing specific gas molecules, which is significant to the sensing performances of gas sensor. In this work, amido-graphene oxide (GO-NH2) loaded poly(ethyleneimine) (PEI) composite thin film (PEI/GO-NH2) with abundant amino functional groups -NH2 was successfully prepared on quartz crystal microbalance (QCM) by a combined spraying and drop coating method for acetone detection at room temperature (25°C). The morphological, spectrographic and acetone-sensing properties of composite film were investigated. The results demonstrated that a wrinkled surface morphology was formed and the ratio of nucleophilic -NH2 was increased for PEI/GO-NH2 composite film. Meanwhile, the composite film sensor possessed excellent acetone-sensing performances, and its sensitivity was about 4.2 times higher than that of pure PEI one owing to the increased -NH2 groups. This study reveals the important role of absorbing favorable functional groups and provides a novel method for the rational design and construction of acetone-sensing materials.

The development of optical systems is heading to multi-branch circuit design and miniaturization. A beam splitter is a common device for dividing an incident beam into two separate beams. Conventional beam splitters are constructed using coated prisms or glass plate. Their bulky size, right-angled output direction, and fixed splitting ratio greatly limit the design of optical arrangement and also hinder the system integration. Here, an all-dielectric metasurface composed of symmetric nano-rings as a beam splitter are designed by Finite-Difference Time-Domain method. By changing the inner and outer radiuses of the nano-rings, the wavefront phase of the emergence beam can be adjusted to form a phase gradient, and the incident beam of arbitrary polarization is divided into two beams according to the designed transmittance and angle. The initial phase of the emergence beam can be changed by adjusting the refractive index of the substrate or adding the silicon film to the substrate, and the splitting ratio can be adjusted from 0.5:1 to 1:1. The simulation demonstrates that the metasurface-based beam splitter is independent of polarization and the power efficiency is over 92% with a compact area of 33.6 μm × 33.6 μm. This compact metasurface-based beam splitter has promising potential for enabling new types of compact optical systems and advancing metasurface-based functional integrated photonic applications.

The charge density wave (CDW) in 1 T –TiSe _2 harbors a nontrivial symmetry configuration. It is important to understand this underlying symmetry both for gaining a handle on the mechanism of CDW formation and for probing the CDW experimentally. Here, based on first-principles computations within the framework of the density functional theory, we unravel the connection between the symmetries of the normal and CDW states and the electronic structure of 1 T –TiSe _2 . Our analysis highlights the key role of irreducible representations of the electronic states and the occurrence of band gaps in the system in driving the CDW. By showing how symmetry-related topology can be obtained directly from the electronic structure, our study provides a practical pathway in search of topological CDW insulators.

Black phosphorus (BP), a new two-dimensional (2D) material, has been deeply developed for extensive applications in electronics and optoelectronics due to its similar physical structure to graphene and thickness dependent direct band gap. Here, we demonstrated a submicrosecond passive Q-switching Er-doped fiber laser with BP as saturable absorber (SA). The BP saturable absorber was fabricated by mechanical exfoliation method. By taking full advantage of the ultrafast relaxation time of BP-SA and careful design of compact ring cavity, we obtained stable Q-switching pulses output with a shortest duration as narrow as 742 ns. With increasing the pump power, the pulse repetition rate accreted gradually almost linearly from 9.78 to 61.25 kHz, and the pulse duration declined rapidly at lower pump power regime and retained approximate stationary at higher pump power regime from 3.05 to 0.742 μs. The experimental results indicate that BP-SA can be an effective SA for nanosecond Q-switching pulse generation.