Engineering Topological Spin Hall Effect in 2D Multiferroic Material.

Topological spin Hall effect (TSHE), promoted by coupling between noncoplanar spins and real-space topology, is a significant phenomenon in condensed matter physics. However, the control of TSHE characteristics is missing due to its intrinsic robustness, and such fundamental difficulty prevents it from being used for spintronics up to now. Here, a rational design approach is demonstrated to engineer TSHE in a controllable and reversible fashion. Through symmetry and model analysis, it is unveiled that antiferromagnetic topological charge, as well as Lorentz forces, acted on conduction electrons, can be coupled with Dzyaloshinskii-Moriya interaction chirality for antiferromagnetic bimerons in 2D multiferroic materials. Such coupling guarantees the ferroelectric control of TSHE. Using first-principles calculations and atomic spin model simulations, the validity of this mechanism is further demonstrated in multiferroic monolayer CuCr2Se4 with experimental feasibility. The alter-chirality of the Dzyaloshinskii-Moriya interaction is found to play a crucial role in realizing this mechanism. This results extend TSHE to be used in spintronics and open a new direction for spintronics research.

Atypical breathing driven two-dimensional valley multiferroicity.

Valley multiferroicity, coupled with ferro-valleytricity and primary ferroicities in a single phase, is of fundamental significance in condensed-matter physics and materials science, as it provides a convenient route to reverse the anomalous valley Hall (AVH) effect. Current research in this field focuses mainly on ferromagnetic ferro-valleytricity, whereas ferroelectric ferro-valleytricity is seldom explored. Here, using symmetry arguments and tight-binding model analysis, we report a novel mechanism of coupling ferro-valleytricity with ferroelectricity, i.e., single-phase valley multiferroicity, in a two-dimensional magnetic lattice. This mechanism correlates to the atypical breathing nature of the magnetic lattice. Importantly, the valley physics, associated with Berry curvature, can be reversed under a ferroelectric transition, thereby guaranteeing the ferroelectrically reversible AVH effect. The underlying physics are discussed in detail. Based on first-principles calculations, we further confirm valley multiferroicity in a real 2D magnetic material of single-layer Gd2CO2. The explored phenomena and mechanism are not only useful for fundamental research in valley multiferroics but also enable a wide range of applications in nanodevices.

Single-Particle Fluorescence Spectroscopy for Elucidating Charge Transfer and Catalytic Mechanisms on Nanophotocatalysts.

Photocatalysis is a cost-effective approach to producing renewable energy. A thorough comprehension of carrier separation at the micronano level is crucial for enhancing the photochemical conversion capabilities of photocatalysts. However, the heterogeneity of photocatalyst nanoparticles and complex charge migration processes limit the profound understanding of photocatalytic reaction mechanisms. By establishing the precise interrelationship between microscopic properties and photophysical behaviors of photocatalysts, single-particle fluorescence spectroscopy can elucidate the carrier separation and catalytic mechanism of the photocatalysts in situ, which provides perspectives for improving the photocatalytic efficiency. This Review primarily focuses on the basic principles and advantages of single-particle fluorescence spectroscopy and its progress in the study of plasmonic and semiconductor photocatalysis, especially emphasizing its importance in understanding the charge separation and photocatalytic reaction mechanism, which offers scientific guidance for designing efficient photocatalytic systems. Finally, we summarize and forecast the future development prospects of single-particle fluorescence spectroscopy technology, especially the insights into its technological upgrading.

Robust second-order topological insulator in 2D van der Waals magnet CrI3.

CrI3 offers an intriguing platform for exploring fundamental physics and the innovative design of spintronics devices in two-dimensional (2D) magnets, and moreover has been instrumental in the study of topological physics. However, the 2D CrI3 monolayer and bilayers have long been thought to be topologically trivial. Here we uncover a hidden facet of the band topology of 2D CrI3 by showing that both the CrI3 monolayer and bilayers are second-order topological insulators (SOTIs) with a nonzero second Stiefel-Whitney number w2 = 1. Furthermore, the topologically nontrivial nature can be explicitly confirmed via the emergence of floating edge states and in-gap corner states. Remarkably, in contrast to most known magnetic topological states, we put forward that the SOTIs in 2D CrI3 monolayer and bilayers are highly robust against magnetic transitions, which remain intact under both ferromagnetic and antiferromagnetic configurations. These interesting predictions not only provide a comprehensive understanding of the band topology of 2D CrI3 but also offer a favorable platform to realize magnetic SOTIs for spintronics applications.

PT Symmetry Breaking Induced Anomalous Valley Hall Effect in 2D Antiferromagnetic Semiconductor.

Realizing the anomalous valley Hall (AVH) effect in two-dimensional (2D) materials is of crucial importance for information processing and recording technology. While the research in this field mainly focuses on ferromagnetic systems, little is known about antiferromagnetic systems. Here, using k·p model analysis, we report a novel mechanism of realizing the AVH effect in 2D antiferromagnetic materials. This physics is related to the PT symmetry breaking induced by intrinsic staggered sublattice potential, which is introduced by asymmetric magnetic ions located at different sublattices. With reversal of the magnetic orientation on different sublattices, the AVH effect can be reversed. Based on first-principles calculations, we further demonstrate this mechanism in an antiferromagnetic monolayer of NiRuCl6. Intriguingly, due to the d orbital mismatch near the Fermi level, monolayer NiRuCl6 simultaneously owns zero net magnetization and large spin splitting and valley polarizations, which facilitates the observation of the AVH effect. Our findings greatly enrich the research on valley physics in antiferromagnetic systems.

High-Temperature Excitonic Condensation in 2D Lattice.

Exploration of high-temperature bosonic condensation is of significant importance for the fundamental many-body physics and applications in nanodevices, which, however, remains a huge challenge. Here, in combination of many-body perturbation theory and first-principles calculations, a new-type spatially indirect exciton can be optically generated in two-dimensional (2D) Bi2S2Te because of its unique structure feature. In particular, the spin-singlet spatially indirect excitons in Bi2S2Te monolayer are dipole/parity allowed and reveal befitting characteristics for excitonic condensation, such as small effective mass and satisfied dilute limitation. Based on the layered Bi2S2Te, the possibility of the high-temperature excitonic Bose-Einstein condensation (BEC) and superfluid state in two dimensions, which goes beyond the current paradigms in both experiment and theory, are proved. It should be highlighted that record-high phase transition temperatures of 289.7 and 72.4 K can be theoretically predicted for the excitonic BEC and superfluidity in the atomic thin Bi2S2Te, respectively. It therefore can be confirmed that Bi2S2Te featuring bound bosonic states is a fascinating 2D platform for exploring the high-temperature excitonic condensation and applications in such as quantum computing and dissipationless nanodevices.

Single-Particle Imaging Photoinduced Charge Transfer of Ferroelectric Polarized Heterostructures for Photocatalysis.

Piezoelectric-assisted photocatalysis has a huge potential in solving the energy shortage and environmental pollution problems, and imaging their detailed charge-transfer process can provide in-depth understanding for the development of high-active piezo-photocatalysts; however, it is still challenging. Herein, topotactic heterostructures of TiO2@BaTiO3 (TO@BTO-S) were constructed by the epitaxial growth of ferroelectric BaTiO3 mesocrystals on TiO2-{001} facets, resulting in a ferroelectric photocatalyst with a polarization orientation on the surface. Notably, the photoinduced charge transfer in ferroelectric TiO2@BaTiO3 was accurately monitored and directly visualized at the single-particle level by the advanced photoluminescence (PL) imaging microscopy systems. The longer PL lifetime of TO@BTO-S demonstrated the efficient charge separation caused by a built-in electric field, which is constructed by the polarization orientation of BaTiO3 mesocrystals. Therefore, the TO@BTO-S heterostructure exhibits efficient piezoelectric-assisted photocatalytic pure water splitting, which is 290 times higher than photocatalysis. This work revealed time/spatial-resolved photoinduced charge transfer in piezoelectric assistance photocatalysts at the single-particle level and demonstrated the great role of polarization orientation in promoting charge transfer for photocatalysis.

Facile Synthesis of a Layered Bismuth-Based MOF With Superhydrophobic-Oleophilic Property and High Oil-Water Separation Performance.

Metal organic frameworks (MOFs) are a class of potential superhydrophobic-oleophilic materials. The organic ligands in superhydrophobic MOFs usually contain long alkyl chains, fluorine groups or aromatic rings with large π conjugation, the preparation of which suffers from high cost, complex operation and so on. In addition, the topological structure of MOFs plays an important role in the hydrophobicity, which may be ignored previously. Here we report a superhydrophobic-oleophilic MOF (BiPPA2) obtained by a facile and fast method, which not only displays a large water contact angle of up to 163° and a small sliding angle of nearly equal to 0°, but also exhibits high sorption capacity for multiple oils and organic solvents, well reusability and high oil retention. In addition, BiPPA2 is stable in a wide pH range (0.5-11.0). Finally, the single crystal structure of BiPPA2 is resolved to reveal the intrinsic reason for the super-hydrophobicity. This work may inspire the further design of pristine superhydrophobic MOFs based on a simple method, which enriches the family of superhydrophobic MOFs and has great significance for practical applications.

Ferrovalleytricity in a two-dimensional antiferromagnetic lattice.

Control over and manipulation of valley physics via ferrovalleytricity is highly desirable for advancing valleytronics. Current research focuses primarily on two-dimensional ferromagnetic systems, while antiferromagnetic counterparts are seldom explored. Here, we present a general mechanism for extending the ferrovalleytricity paradigm to antiferromagnetic lattices to achieve spin control over valley physics. Our symmetry analysis and k·p model reveal that by introducing a Zeeman field aroused by the proximity effect, spin-switchable non-uniform potential is imposed on the two sublattices of an antiferromagnetic lattice. This enables spin control over the anomalous valley Hall effect, thereby realizing ferrovalleytricity. This mechanism is confirmed in a CrBr3-MnPSe3-CrBr3 heterotrilayer from first principles, where the spin-switchable non-uniform Zeeman effect is exerted on two Mn sublattices when the antiferromagnetic MnPSe3 layer is sandwiched between ferromagnetic CrBr3 layers. Such a non-uniform Zeeman effect combined with valley physics guarantees spin control over the anomalous valley Hall effect, i.e., ferrovalleytricity, in the MnPSe3 layer. Our work will shed light on potential applications of valley physics in antiferromagnetic systems.

Mesostructure-Specific Configuration of *CO Adsorption for Selective CO2 Electroreduction to C2+ Products.

The multi-carbon (C2+) alcohols produced by electrochemical CO2 reduction, such as ethanol and n-propanol, are considered as indispensable liquid energy carriers. In most C-C coupling cases, however, the concomitant gaseous C2H4 product results in the low selectivity of C2+ alcohols. Here, we report rational construction of mesostructured CuO electrocatalysts, specifically mesoporous CuO (m-CuO) and cylindrical CuO (c-CuO), enables selective distribution of C2+ products. The m-CuO and c-CuO show similar selectivity towards total C2+ products (≥76 %), but the corresponding predominant products are C2+ alcohols (55 %) and C2H4 (52 %), respectively. The ordered mesostructure not only induces the surface hydrophobicity, but selectively tailors the adsorption configuration of *CO intermediate: m-CuO prefers bridged adsorption, whereas c-CuO favors top adsorption as revealed by in situ spectroscopies. Computational calculations unravel that bridged *CO adsorbate is prone to deep protonation into *OCH3 intermediate, thus accelerating the coupling of *CO and *OCH3 intermediates to generate C2+ alcohols; by contrast, top *CO adsorbate is apt to undergo conventional C-C coupling process to produce C2H4. This work illustrates selective C2+ products distribution via mesostructure manipulation, and paves a new path into the design of efficient electrocatalysts with tunable adsorption configuration of key intermediates for targeted products.

Strain-driven skyrmion-bimeron switching in topological magnetic monolayer CrSeBr.

Skyrmion-bimeron switching is one of the most important phenomena in topological magnetism. Currently, it is usually realized by the annoying spin orientation vertical-reversal through magnetic field. Based on first-principles calculations and atomic spin simulations, we alternatively unveil that the switching between magnetic skyrmions and bimerons can be achieved in topological magnetic monolayer CrSeBr by external strain. The core mechanism of this switching is traced to the controllable magnetic anisotropy of monolayer CrSeBr influenced by the strain-engineered low-energy states around the Fermi level. We also introduce a parameter |κ| as a criterion for judging the stability of magnetic skyrmions and bimerons, which can be adopted as a useful descriptor linking the presence of skyrmion-bimeron switching driven by strain. The underlying physics is discussed in detail. The predicted strain controlled skyrmion-bimeron switching may be interesting for topological magnetic devices.

Photocatalytic Overall Water Splitting with a Solar-to-Hydrogen Conversion Efficiency Exceeding 2 % through Halide Perovskite.

Photocatalytic water splitting using semiconductors is a promising approach for converting solar energy to clean energy. However, challenges such as sluggish water oxidation kinetics and limited light absorption of photocatalyst cause low solar-to-hydrogen conversion efficiency (STH). Herein, we develop a photocatalytic overall water splitting system using I3 -/I- as the shuttle redox couple to bridge the H2-producing half-reaction with the O2-producing half-reaction. The system uses the halide perovskite of benzylammonium lead iodide (PMA2PbI4, PMA=C6H5CH2NH2) loaded with MoS2 (PMA2PbI4/MoS2) as the H2 evolution photocatalyst, and the RuOx-loaded WO3 (WO3/RuOx) as the O2 evolution photocatalyst, achieving a H2/O2 production in stoichiometric ratio with an excellent STH of 2.07 %. This work provides a detour route for photocatalytic water splitting with the help of I3 -/I- shuttle redox couple in the halide perovskite HI splitting system and enlightens one to integrate and utilize multi catalytic strategies for solar-driven water splitting.

Ferroelectrovalley in Two-Dimensional Multiferroic Lattices.

Engineering the valley index is essential and highly sought for valley physics, but currently, it is exclusively based on the paradigm of the challenging ferrovalley with spin-orientation reversal under a magnetic field. Here, an alternative strategy, i.e., the so-called ferroelectrovalley, is proposed to tackle the insurmountable spin-orientation reversal, which reverses the valley index with the feasible ferroelectricity. Using symmetry arguments and the tight-binding model, the C2z rotation is unveiled to be able to take the place of time reversal for operating the valley index in two-dimensional multiferroic kagome lattices, which enables a ferroelectricity-engineered valley index, thereby generating the concept of a ferroelectrovalley. Based on first-principles calculations, this concept is further demonstrated in the breathing kagome lattice of single-layer Ti3Br8, wherein ferroelectricity couples with the breathing process. These findings open a new direction for valleytronics and 2D materials research.

Full-spectrum plasmonic semiconductors for photocatalysis.

Localized surface plasmon resonance (LSPR) of noble metal nanoparticles can focus surrounding light onto the particle surface to boost photochemical reactions and solar energy utilization. However, the rarity and high cost of noble metals limit their applications in plasmonic photocatalysis, forcing researchers to seek low-cost alternatives. Recently, some heavily doped semiconductors with high free carrier density have garnered attention due to their metal-like LSPR properties. However, plasmonic semiconductors have complex surface structures characterized by the presence of a depletion layer, which poses challenges for active site exposure and hot carrier transfer, resulting in low photocatalytic activity. In this review, we introduce the essential characteristics and types, synthesis methods, and characterization techniques of full-spectrum plasmonic semiconductors, elucidate the mechanism of full-spectrum nonmetallic plasmonic photocatalysis, including the local electromagnetic field, hot carrier generation and transfer, the photothermal effect, and the solutions for the surface depletion layer, and summarize the applications of plasmonic semiconductors in photocatalytic environmental remediation, CO2 reduction, H2 generation, and organic transformations. Finally, we provide a perspective on full-spectrum plasmonic photocatalysis, aiming to guide the design and development of plasmonic photocatalysts.

Plasmon-Driven Highly Selective CO2 Photoreduction to C2H4 on Ionic Liquid-Mediated Copper Nanowires.

Selective CO2 photoreduction to value-added multi-carbon (C2+) feedstocks, such as C2H4, holds great promise in direct solar-to-chemical conversion for a carbon-neutral future. Nevertheless, the performance is largely inhibited by the high energy barrier of C-C coupling process, thereby leading to C2+ products with low selectivity. Here we report that through facile surface immobilization of a 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIM-BF4) ionic liquid, plasmonic Cu nanowires could enable highly selective CO2 photoreduction to C2H4 product. At an optimal condition, the resultant plasmonic photocatalyst exhibits C2H4 production with selectivity up to 96.7 % under 450 nm monochromatic light irradiation, greatly surpassing its pristine Cu counterpart. Combined in situ spectroscopies and computational calculations unravel that the addition of EMIM-BF4 ionic liquid modulates the local electronic structure of Cu, resulting in its enhanced adsorption strength of *CO intermediate and significantly reduced energy barrier of C-C coupling process. This work paves new path for Cu surface plasmons in selective artificial photosynthesis to targeted products.

Enhanced Photocatalytic Ozonation Using Modified TiO2 With Designed Nucleophilic and Electrophilic Sites.

Photocatalytic ozonation is considered to be a promising approach for the treatment of refractory organic pollutants, but the design of efficient catalyst remains a challenge. Surface modification provides a potential strategy to improve the activity of photocatalytic ozonation. In this work, density functional theory (DFT) calculations were first performed to check the interaction between O3 and TiO2-OH (surface hydroxylated TiO2) or TiO2-F (surface fluorinated TiO2), and the results suggest that TiO2-OH displays better O3 adsorption and activation than does TiO2-F, which is confirmed by experimental results. The surface hydroxyl groups greatly promote the O3 activation, which is beneficial for the generation of reactive oxygen species (ROS). Importantly, TiO2-OH displays better performance towards pollutants (such as berberine hydrochloride) removal than does TiO2-F and most reported ozonation photocatalysts. The total organic carbon (TOC) removal efficiency reaches 84.4 % within two hours. This work highlights the effect of surface hydroxylation on photocatalytic ozonation and provides ideas for the design of efficient photocatalytic ozonation catalysts.

Sliding Ferroelectricity Engineered Coupling between Spin Hall Effect and Layertronics in 2D Lattice.

Coupling the spin Hall effect with novel degrees of freedom of electrons is central to the rich phenomena observed in condensed-matter physics. Here, using symmetry analysis and a low-energy k·p model, we report the sliding ferroelectricity engineered coupling between spin Hall effect and emerging layertronics, thereby generating the layer spin Hall effect (LSHE), in a 2D lattice. The physics is rooted in a pair of T-symmetry connected valleys, which experience spin splitting accompanied by large Berry curvature under spin-orbit coupling. The interaction between the out-of-plane ferroelectricity and electronic properties gives rise to the layer-locked Berry curvature and thus layer-polarized spin Hall effect (LP-SHE) in the bilayers. Such LP-SHE is strongly coupled with sliding ferroelectricity, enabling it to be ferroelectrically reversible. Using first-principles calculations, the mechanism is further demonstrated in a series of real bilayer systems, including MoS2, MoTe2, WSe2, MoSi2P4, and MoSi2As4. These phenomena and insights open a new direction for spin Hall effect.

Non-Metal Sulfur Doping of Indium Hydroxide Nanocube for Selectively Photocatalytic Reduction of CO2 to CH4: A "One Stone Three Birds" Strategy.

Photocatalytic CO2 reduction is considered as a promising strategy for CO2 utilization and producing renewable energy, however, it remains challenge in the improvement of photocatalytic performance for wide-band-gap photocatalyst with controllable product selectivity. Herein, the sulfur-doped In(OH)3 (In(OH)xSy-z) nanocubes are developed for selective photocatalytic reduction of CO2 to CH4 under simulated light irradiation. The CH4 yield of the optimal In(OH)xSy-1.0 can be enhanced up to 39 times and the CH4 selectivity can be regulated as high as 80.75% compared to that of pristine In(OH)3. The substitution of sulfur atoms for hydroxyl groups in In(OH)3 enhances the visible light absorption capability, and further improves the hydrophilicity behavior, which promotes the H2O dissociation into protons (H*) and accelerates the dynamic proton-feeding CO2 hydrogenation. In situ DRIFTs and DFT calculation confirm that the non-metal sulfur sites significantly weaken the over-potential of the H2O oxidation and prevent the formation of ·OH radicals, enabling the stabilization of *CHO intermediates and thus facilitating CH4 production. This work highlights the promotion effect of the non-metal doping engineering on wide-band-gap photocatalysts for tailoring the product selectivity in photocatalytic CO2 reduction.

Floquet engineering of the orbital Hall effect and valleytronics in two-dimensional topological magnets.

We show that circularly polarized light is a versatile way to manipulate both the orbital Hall effect and band topology in two-dimensional ferromagnets. Employing the hexagonal lattice, we proposed that interactions between light and matter allow for the modulation of the valley polarization effect, and then band inversions, accompanied by the band gap closing and reopening processes, can be achieved subsequently at two valleys. Remarkably, the distribution of orbital angular momentum can be controlled by the band inversions, leading to the Floquet engineering of the orbital Hall effect, as well as the topological phase transition from a second-order topological insulator to a Chern insulator with in-plane magnetization, and then to a normal insulator. Furthermore, first-principles calculations validate the feasibility with the 2H-ScI2 monolayer as a candidate material, paving a technological avenue to bridge the orbitronics and nontrivial topology using Floquet engineering.

Coupled Electronic and Magnonic Topological States in Two-Dimensional Ferromagnets.

Magnetic materials offer a fertile playground for fundamental physics discovery, with not only electronic but also magnonic topological states intensively explored. However, one natural material with both electronic and magnonic nontrivial topologies is still unknown. Here, we demonstrate the coexistence of first-order topological magnon insulators (TMIs) and electronic second-order topological insulators (SOTIs) in 2D honeycomb ferromagnets, giving rise to the nontrivial corner states being connected by the charge-free magnonic edge states. We show that, with C3 symmetry, the phase factor ± ϕ caused by the next nearest-neighbor Dzyaloshinskii-Moriya interaction breaks the pseudo-spin time-reversal symmetry T, which leads to the split of magnon bands, i.e., the emergence of TMIs with a nonzero Chern number of C=-1, in experimentally feasible candidates of MoI3, CrSiTe3, and CrGeTe3 monolayers. Moreover, protected by the C3 symmetry, the electronic SOTIs characterized by nontrivial corner states are obtained, bridging the topological aspect of fermions and bosons with a high possibility of innovative applications in spintronics devices.