Homogenizing out-of-plane cation composition in perovskite solar cells.

Perovskite solar cells with the formula FA1-xCsxPbI3, where FA is formamidinium, provide an attractive option for integrating high efficiency, durable stability and compatibility with scaled-up fabrication. Despite the incorporation of Cs cations, which could potentially enable a perfect perovskite lattice1,2, the compositional inhomogeneity caused by A-site cation segregation is likely to be detrimental to the photovoltaic performance of the solar cells3,4. Here we visualized the out-of-plane compositional inhomogeneity along the vertical direction across perovskite films and identified the underlying reasons for the inhomogeneity and its potential impact for devices. We devised a strategy using 1-(phenylsulfonyl)pyrrole to homogenize the distribution of cation composition in perovskite films. The resultant p-i-n devices yielded a certified steady-state photon-to-electron conversion efficiency of 25.2% and durable stability.

Layer-dependent correlated phases in WSe2/MoS2 moiré superlattice.

Electron correlation plays an essential role in the macroscopic quantum phenomena in the moiré heterostructure, such as antiferromagnetism and correlated insulating phases. Unlike the phenomena where the interaction involves only electrons in one layer, the interaction of distinct phases in two or more layers represents a new horizon forward, such as the one in the Kondo lattice model. Here, using interlayer excitons as a probe, we show that the interlayer interactions in heterobilayers of tungsten diselenide and molybdenum disulfide (WSe2/MoS2) can be electrically switched on and off, resulting in a layer-dependent correlated phase diagram, including single-layer, layer-selective, excitonic-insulator and layer-hybridized regions. We demonstrate that these correlated phases affect the interlayer exciton non-radiative decay pathways. These results reveal the role of strong correlation on interlayer exciton dynamics and pave the way for studying the layer-resolved strong correlation behaviour in moiré heterostructures.

High-Density Coordinatively Unsaturated Zn Catalyst for Efficient Alkane Dehydrogenation.

The exploration of non-noble metal catalysts for alkane dehydrogenation and their catalytic mechanisms is the priority in catalysis research. Here, we report a high-density coordinatively unsaturated Zn cation (Zncus) catalyst for the direct dehydrogenation (DDH) of ethylbenzene (EB) to styrene (ST). The catalyst demonstrated good catalytic performance (∼40% initial EB conversion rate and >98% ST selectivity) and excellent regeneration ability in the reaction, which is attributed to the high-density (HD) distribution and high-stability structure of Zncus active sites on the surface of zinc silicate (HD-Zncus@ZS). Density functional theory (DFT) calculations further illustrated the reaction pathway and intermediates, supporting that the Zncus sites can efficiently activate the C-H bond of ethyl on ethylbenzene. Developing the high-density Zncus catalyst and exploring the catalytic mechanism laid a good foundation for designing practical non-noble metal catalysts.

Low-Temperature Acetylene Semi-Hydrogenation over the Pd1-Cu1 Dual-Atom Catalyst.

The atomically dispersed metal catalyst or single-atom catalyst (SAC) with the utmost metal utilization efficiency shows excellent selectivity toward ethylene compared to the metal nanoparticles catalyst in the acetylene semi-hydrogenation reaction. However, these catalysts normally work at relatively high temperatures. Achieving low-temperature reactivity while preserving high selectivity remains a challenge. To improve the intrinsic reactivity of SACs, rationally tailoring the coordination environments of the first metal atom by coordinating it with a second neighboring metal atom affords an opportunity. Here, we report the fabrication of a dual-atom catalyst (DAC) that features a bonded Pd1-Cu1 atomic pair anchoring on nanodiamond graphene (ND@G). Compared to the single-atom Pd or Cu catalyst, it exhibits increased reactivity at a lower temperature, with 100% acetylene conversion and 92% ethylene selectivity at 110 °C. This work provides a strategy for designing DACs for low-temperature hydrogenation by manipulating the coordination environment of catalytic sites at the atomic level.

Few-Atom Pt Ensembles Enable Efficient Catalytic Cyclohexane Dehydrogenation for Hydrogen Production.

Identification of catalytic active sites is pivotal in the design of highly effective heterogeneous metal catalysts, especially for structure-sensitive reactions. Downsizing the dimension of the metal species on the catalyst increases the dispersion, which is maximized when the metal exists as single atoms, namely, single-atom catalysts (SACs). SACs have been reported to be efficient for various catalytic reactions. We show here that the Pt SACs, although with the highest metal atom utilization efficiency, are totally inactive in the cyclohexane (C6H12) dehydrogenation reaction, an important reaction that could enable efficient hydrogen transportation. Instead, catalysts enriched with fully exposed few-atom Pt ensembles, with a Pt-Pt coordination number of around 2, achieve the optimal catalytic performance. The superior performance of a fully exposed few-atom ensemble catalyst is attributed to its high d-band center, multiple neighboring metal sites, and weak binding of the product.

Fully-Exposed Pd Cluster Catalyst: An Excellent Catalytic Antibacterial Nanomaterial.

Exploring antibacterial nanomaterials with excellent catalytic antibacterial properties has always been a hot research topic. However, the construction of nanomaterials with robust antibacterial activity at the atomic level remains a great challenge. Here a fully-exposed Pd cluster atomically-dispersed on nanodiamond-graphene (Pdn /ND@G) with excellent catalytic antibacterial properties is reported. The fully-exposed Pd cluster nanozyme provides atomically-dispersed Pd cluster sites that facilitate the activation of oxygen. Notably, the oxidase-like catalytic performance of the fully-exposed Pd cluster nanozyme is much higher than that of Pd single-atom oxidase mimic, Pd nanoparticles oxidase mimic and even the previously reported palladium-based oxidase mimics. Under the density functional theory (DFT) calculations, the Pd cluster sites can efficiently catalyze the decomposition of oxygen to generate reactive oxygen species, resulting in strong antibacterial properties. This research provides a valuable insight to the design of novel oxidase mimic and antibacterial nanomaterial.

Two-Dimensional Antiferroelectricity in Nanostripe-Ordered In_{2}Se_{3}.

Two-dimensional (2D) layered materials have been an exciting frontier for exploring emerging physics at reduced dimensionality, with a variety of exotic properties demonstrated at 2D limit. Here, we report the first experimental discovery of in-plane antiferroelectricity in a 2D material ß^{'}-In_{2}Se_{3}, using optical and electron microscopy consolidated by first-principles calculations. Different from conventional 3D antiferroelectricity, antiferroelectricity in ß^{'}-In_{2}Se_{3} is confined within the 2D layer and generates the unusual nanostripe ordering: the individual nanostripes exhibit local ferroelectric polarization, whereas the neighboring nanostripes are antipolar with zero net polarization. Such a unique superstructure is underpinned by the intriguing competition between 2D ferroelectric and antiferroelectric ordering in ß^{'}-In_{2}Se_{3}, which can be preserved down to single-layer thickness as predicted by calculation. Besides demonstrating 2D antiferroelectricity, our finding further resolves the true nature of the ß^{'}-In_{2}Se_{3} superstructure that has been under debate for over four decades.

Atomically Dispersed Pd on Nanodiamond/Graphene Hybrid for Selective Hydrogenation of Acetylene.

We reported here a strategy to use a defective nanodiamond-graphene (ND@G) to prepare an atomically dispersed metal catalyst, i.e., in the current case atomically dispersed palladium catalyst which is used for selective hydrogenation of acetylene in the presence of abundant ethylene. The catalyst exhibits remarkable performance for the selective conversion of acetylene to ethylene: high conversion (100%), ethylene selectivity (90%), and good stability. The unique structure of the catalyst (i.e., atomically dispersion of Pd atoms on graphene through Pd-C bond anchoring) blocks the formation of unselective subsurface hydrogen species and ensures the facile desorption of ethylene against the overhydrogenation to undesired ethane, which is the key for the outstanding selectivity of the catalyst.

Gate-tunable strong-weak localization transition in few-layer black phosphorus.

Atomically-thin black phosphorus (BP) field-effect transistors show strong-weak localization transition, which is tunable through gate voltages. Hopping transports through charge impurity-induced localized states are observed at low carrier density regime. Variable-range hopping model is applied to simulate scattering behaviors of charge carriers. In the high carrier concentration regime, a negative magnetoresistance indicates weak localization effects. The extracted phase coherence length is power-law temperature-dependent [Formula: see text] and demonstrates inelastic electron-electron interactions and the 2D transport features in few-layer BP field-effect devices. The competition between localization and phase coherence lengths is investigated and analyzed based on observed gate-tunable strong-weak localization transition in few-layer BP.

Moiré Synergy: An Emerging Playground by Coupled Moirés.

Moiré superlattices of tunable wavelengths and the further developed coupled-moiré systems, by artificially assembling two-dimensional (2D) van der Waals (vdW) materials as designed, have brought up a versatile toolbox to explore fascinating condensed matter physics and their stimulating physicochemical functionalities. In this Perspective, we briefly review the recent progress in the emerging field of moiré synergy, highlighting the synergetic effects arising in distinct multi-moiré heterostructures of graphene and transition metal dichalcogenides (TMDCs). A spectrum of coupled-moiré configurations, the advanced characterization, and the exploitation efforts on the moiré-moiré interactions will be discussed. Finally, we look out for urgent challenges to be conquered in the community and some potential research directions in the near future.

Magnetically Tunable Spontaneous Superradiance from Mesoscopic Perovskite Emitter Clusters.

Perovskite emitters are promising materials as next-generation optical sources due to their low fabrication cost and high quantum yield. In particular, the superradiant emission from a few coherently coupled perovskite emitters can be used to produce a bright entangled photon source. Here, we report the observation of superradiance from mesoscopic (<55) CsPbBr3 perovskite emitters, which have a much smaller ensemble size than the previously reported results (>106 emitters). The superradiance is spontaneously generated by off-resonance excitation and detected by time-resolved photoluminescence and second-order photon correlation measurements. We observed a remarkable magnetic tunability of the superradiant photon bunching, indicating a magnetic field-induced decoherence process. The experimental results can be well explained using a theoretical framework based on the microscopic master equation. Our findings shed light on the superradiance mechanism in perovskite emitters and enable low-cost quantum light sources based on perovskite.

Giant nonlinear Hall effect in twisted bilayer WSe2.

The recently discovered nonlinear Hall effect (NHE) in a few non-interacting systems provides a novel mechanism for generating second-harmonic electrical Hall signals under time-reversal-symmetric conditions. Here, we introduce a new approach to engineering an NHE by using twisted moiré structures. We found that the twisted WSe2 bilayer exhibited an NHE when the Fermi level was tuned to the moiré flat bands. When the first moiré band was half-filled, the nonlinear Hall signal exhibited a sharp peak with a generation efficiency that was at least two orders of magnitude greater than those obtained in previous experiments. We discuss the possible origins of the diverging generation efficiency in twisted WSe2 based on resistivity measurements, such as moiré-interface-induced correlation effects and mass-diverging-type continuous Mott transition. This study demonstrates not only how interaction effects can combine with Berry curvature dipoles to produce novel quantum phenomena, but also the potential of NHE measurements as a new tool for studying quantum criticality.

Palladium single-atom catalysts synthesized by a gas-assisted redispersion strategy for efficient benzaldehyde hydrogenation.

A simple and efficient strategy was developed for the synthesis of Pd single-atom catalysts (PdSA/G) by nitric acid vapor-assisted redispersion. The as-prepared PdSA/G displayed robust catalytic performance in the selective hydrogenation reaction of benzaldehyde. This work paves a new way for the design of supported Pd single-atom catalysts.

Epitaxial substitution of metal iodides for low-temperature growth of two-dimensional metal chalcogenides.

The integration of various two-dimensional (2D) materials on wafers enables a more-than-Moore approach for enriching the functionalities of devices1-3. On the other hand, the additive growth of 2D materials to form heterostructures allows construction of materials with unconventional properties. Both may be achieved by materials transfer, but often suffer from mechanical damage or chemical contamination during the transfer. The direct growth of high-quality 2D materials generally requires high temperatures, hampering the additive growth or monolithic incorporation of different 2D materials. Here we report a general approach of growing crystalline 2D layers and their heterostructures at a temperature below 400 °C. Metal iodide (MI, where M = In, Cd, Cu, Co, Fe, Pb, Sn and Bi) layers are epitaxially grown on mica, MoS2 or WS2 at a low temperature, and the subsequent low-barrier-energy substitution of iodine with chalcogens enables the conversion to at least 17 different 2D crystalline metal chalcogenides. As an example, the 2D In2S3 grown on MoS2 at 280 °C exhibits high photoresponsivity comparable with that of the materials grown by conventional high-temperature vapour deposition (~700-1,000 °C). Multiple 2D materials have also been sequentially grown on the same wafer, showing a promising solution for the monolithic integration of different high-quality 2D materials.

Structure-dependence and metal-dependence on atomically dispersed Ir catalysts for efficient n-butane dehydrogenation.

Single-site pincer-ligated iridium complexes exhibit the ability for C-H activation in homogeneous catalysis. However, instability and difficulty in catalyst recycling are inherent disadvantages of the homogeneous catalyst, limiting its development. Here, we report an atomically dispersed Ir catalyst as the bridge between homogeneous and heterogeneous catalysis, which displays an outstanding catalytic performance for n-butane dehydrogenation, with a remarkable n-butane reaction rate (8.8 mol·gIr-1·h-1) and high butene selectivity (95.6%) at low temperature (450 °C). Significantly, we correlate the BDH activity with the Ir species from nanoscale to sub-nanoscale, to reveal the nature of structure-dependence of catalyst. Moreover, we compare Ir single atoms with Pt single atoms and Pd single atoms for in-depth understanding the nature of metal-dependence at the atomic level. From experimental and theoretical calculations results, the isolated Ir site is suitable for both reactant adsorption/activation and product desorption. Its remarkable dehydrogenation capacity and moderate adsorption behavior are the key to the outstanding catalytic activity and selectivity.

In-plane charged antiphase boundary and 180° domain wall in a ferroelectric film.

The deterministic creation and modification of domain walls in ferroelectric films have attracted broad interest due to their unprecedented potential as the active element in non-volatile memory, logic computation and energy-harvesting technologies. However, the correlation between charged and antiphase states, and their hybridization into a single domain wall still remain elusive. Here we demonstrate the facile fabrication of antiphase boundaries in BiFeO3 thin films using a He-ion implantation process. Cross-sectional electron microscopy, spectroscopy and piezoresponse force measurement reveal the creation of a continuous in-plane charged antiphase boundaries around the implanted depth and a variety of atomic bonding configurations at the antiphase interface, showing the atomically sharp 180° polarization reversal across the boundary. Therefore, this work not only inspires a domain-wall fabrication strategy using He-ion implantation, which is compatible with the wafer-scale patterning, but also provides atomic-scale structural insights for its future utilization in domain-wall nanoelectronics.

Interlayer donor-acceptor pair excitons in MoSe2/WSe2 moiré heterobilayer.

Localized interlayer excitons (LIXs) in two-dimensional moiré superlattices exhibit sharp and dense emission peaks, making them promising as highly tunable single-photon sources. However, the fundamental nature of these LIXs is still elusive. Here, we show the donor-acceptor pair (DAP) mechanism as one of the origins of these excitonic peaks. Numerical simulation results of the DAP model agree with the experimental photoluminescence spectra of LIX in the moiré MoSe2/WSe2 heterobilayer. In particular, we find that the emission energy-lifetime correlation and the nonmonotonic power dependence of the lifetime agree well with the DAP IX model. Our results provide insight into the physical mechanism of LIX formation in moiré heterostructures and pave new directions for engineering interlayer exciton properties in moiré superlattices.

Promoting Dinuclear-Type Catalysis in Cu1 -C3 N4 Single-Atom Catalysts.

Reducing particle size in supported metal catalysts to single-atom level isolates the active metal sites and maximizes the atomic utilization efficiency. However, the large inter-atom distance, particularly in low-loading single-atom catalyst (SAC), is not favorable for a complex reaction where two (or more) reactants have to be activated. A key question is how to control the inter-atom distances to promote dinuclear-type coactivation at the adjacent metal sites. Here, it is reported that reducing the average inter-atom distance of copper SACs supported on carbon nitride (C3 N4 ) to 0.74 ± 0.13 nm allows these catalysts to exhibit a dinuclear-type catalytic mechanism in the nitrile-azide cycloaddition. Operando X-ray absorption fine structure study reveals a dynamic ligand exchange process between nitrile and azide, followed by their coactivation on dinuclear Cu SAC sites to form the tetrazole product. This work highlights that reducing the nearest-neighbor distance of SAC allows the mechanistic pathway to diversify from single-site to multisite catalysis.

A Magnetically Separable Pd Single-Atom Catalyst for Efficient Selective Hydrogenation of Phenylacetylene.

Selective hydrogenation of alkynes to alkenes plays a crucial role in the synthesis of fine chemicals. However, how to achieve high selectivity and effective separation of the catalyst and substrate while obtaining high activity is the key for this reaction. In this work, a Pd single-atom catalyst is anchored to the shell of magnetic core-shell particles that consist of a Ni-nanoparticles core and a graphene sheets shell (Ni@G) for semi-hydrogenation of phenylacetylene, delivering 93% selectivity to styrene at full conversion with a robust turnover frequency of 7074 h-1 under mild reaction conditions (303 K, 2 bar H2 ). Moreover, the catalyst can be recovered promptly from the liquid phase due to its magnetic separability, which makes it present good stability for enduring five cycles. Experimental and theoretical investigations reveal that H2 and substrates are activated by atomically dispersed Pd atoms and Ni@G hybrid support, respectively. The hydrogenation reaction occurs on the surface of Ni@G via hydrogen spillover from the metal to the support. Such a strategy opens an avenue for designing highly active, selective, and magnetically recyclable catalysts for selective hydrogenation in liquid reaction systems.