Does a Higher Density of Active Sites Indicate a Higher Reaction Rate?

A consensus view in catalysis is that a higher density of catalytically active sites indicates a higher reaction rate. Using molecular dynamics simulations capable of mimicking the electrochemical formation of gas molecules, we herein demonstrate that this view is problematic for electrocatalytic gas production. Our simulation results show that a higher density of catalytic active sites does not necessarily indicate a higher reaction rate─a high density of active sites could lead to a reduction in the rate of reaction. Further analysis reveals that this abnormal phenomenon is ascribed to aggregation of the produced gas molecules near catalytic sites. This work challenges the consensus view and lays the groundwork for better developing gas-producing reaction electrocatalysts.

Scalable integration of hybrid high-κ dielectric materials on two-dimensional semiconductors.

Two-dimensional (2D) semiconductors are promising channel materials for next-generation field-effect transistors (FETs). However, it remains challenging to integrate ultrathin and uniform high-κ dielectrics on 2D semiconductors to fabricate FETs with large gate capacitance. We report a versatile two-step approach to integrating high-quality dielectric film with sub-1 nm equivalent oxide thickness (EOT) on 2D semiconductors. Inorganic molecular crystal Sb2O3 is homogeneously deposited on 2D semiconductors as a buffer layer, which forms a high-quality oxide-to-semiconductor interface and offers a highly hydrophilic surface, enabling the integration of high-κ dielectrics via atomic layer deposition. Using this approach, we can fabricate monolayer molybdenum disulfide-based FETs with the thinnest EOT (0.67 nm). The transistors exhibit an on/off ratio of over 106 using an ultra-low operating voltage of 0.4 V, achieving unprecedently high gating efficiency. Our results may pave the way for the application of 2D materials in low-power ultrascaling electronics.

On the Working Mechanisms of Molecules-Based Van der Waals Dielectrics.

Sb2 O3 molecules offer unprecedented opportunities for the integration of a van der Waals (vdW) dielectric and a 2D vdW semiconductor. However, the working mechanisms underlying molecules-based vdW dielectrics remain unclear. Here, the working mechanisms of Sb2 O3 and two Sb2 O3 -like molecules (As2 O3 and Bi2 O3 ) as dielectrics are systematically investigated by combining first-principles calculations and gate leakage current theories. It is revealed that molecules-based vdW dielectrics have a considerable advantage over conventional dielectric materials: defects hardly affect their insulating properties. This shows that it is unnecessary to synthesize high-quality crystals in practical applications, which has been a long-standing challenge for conventional dielectric materials. Further analysis reveals that a large thermionic-emission current renders Sb2 O3 difficult to simultaneously satisfy the requirements of dielectric layers in p-MOS and n-MOS, which hinders its application for complementary metal-oxide-semiconductor (CMOS) devices. Remarkably, it is found that As2 O3 can serve as a dielectric for both p-MOS and n-MOS. This work not only lays a theoretical foundation for the application of molecules-based vdW dielectrics, but also offers an unprecedentedly competitive dielectric (i.e., As2 O3 ) for 2D vdW semiconductors-based CMOS devices, thus having profound implications for future semiconductor industry.

Atomically Dispersed Uranium Enables an Unprecedentedly High NH3 Yield Rate.

The low NH3 yield rate is a grand challenge for electrocatalytic N2 reduction to NH3. Herein, we report the first uranium single-atom catalyst (SAC) capable of catalyzing the electrochemical N2 reduction reaction (NRR). The uranium SAC features a low limiting potential (<0.5 V) and near-zero free energy changes for N2 adsorption and NH3 desorption. The integration of these merits enables the uranium SAC to afford an unprecedentedly high NH3 yield rate, 3-4 orders of magnitude higher than that of the Ru(0001) surface, which is widely recognized as an excellent NRR electrocatalyst. Further theoretical analysis reveals that the N2 reduction catalyzed by the uranium SAC is synergistically regulated by the d and f electrons of atomic uranium. This work proposes a promising solution (that is, atomically dispersed uranium) to the daunting challenge associated with the low NH3 yield rate, thus enabling the scalable production of NH3 via electrochemical N2 reduction.

An Ultrathin Inorganic Molecular Crystal Interfacial Layer for Stable Zn Anode.

Zn metal anode suffers from dendrite growth and side reactions during cycling, significantly deteriorating the lifespan of aqueous Zn metal batteries. Herein, we introduced an ultrathin and ultra-flat Sb2 O3 molecular crystal layer to stabilize Zn anode. The in situ optical and atomic force microscopes observations show that such a 10 nm Sb2 O3 thin layer could ensure uniform under-layer Zn deposition with suppressed tip growth effect, while the traditional WO3 layer undergoes an uncontrolled up-layer Zn deposition. The superior regulation capability is attributed to the good electronic-blocking ability and low Zn affinity of the molecular crystal layer, free of dangling bonds. Electrochemical tests exhibit Sb2 O3 layer can significantly improve the cycle life of Zn anode from 72 h to 2800 h, in contrast to the 900 h of much thicker WO3 even in 100 nm. This research opens up the application of inorganic molecular crystals as the interfacial layer of Zn anode.

Giant Tunability of Charge Transport in 2D Inorganic Molecular Crystals by Pressure Engineering.

The unique intermolecular van der Waals force in emerging two-dimensional inorganic molecular crystals (2DIMCs) endows them with highly tunable structures and properties upon applying external stimuli. Using high pressure to modulate the intermolecular bonding, here we reveal the highly tunable charge transport behavior in 2DIMCs for the first time, from an insulator to a semiconductor. As pressure increases, 2D α-Sb2 O3 molecular crystal undergoes three isostructural transitions, and the intermolecular bonding enhances gradually, which results in a considerably decreased band gap by 25 % and a greatly enhanced charge transport. Impressively, the in situ resistivity measurement of the α-Sb2 O3 flake shows a sharp drop by 5 orders of magnitude in 0-3.2 GPa. This work sheds new light on the manipulation of charge transport in 2DIMCs and is of great significance for promoting the fundamental understanding and potential applications of 2DIMCs in advanced modern technologies.

Van der Waals Epitaxy of Bi2 Te2 Se/Bi2 O2 Se Vertical Heterojunction for High Performance Photodetector.

Bismuth oxyselenide (Bi2 O2 Se) has emerged as a promising candidate for electronic and optoelectronic applications due to its outstanding electron mobility and ambient stability. However, high dark current and relatively slow photoresponse that originate from high charge carrier concentration as well as bolometric effect in Bi2 O2 Se inhibit further improvement of Bi2 O2 Se based photodetectors. Here, a one-step van der Waals (vdW) epitaxy synthesis of Bi2 Te2 Se/Bi2 O2 Se vertical heterojunction with type-II band alignment and high-quality interface is demonstrated. The crystal quality and uniformity of the heterojunction are supported by Raman, transmission electron microscopy and energy dispersive spectroscopy results. A photodetector based on Bi2 Te2 Se/Bi2 O2 Se heterojunction demonstrates steady photoresponse over a large wavelength range (532-1456 nm), with a high specific responsivity of 2.21 × 103 A W-1 at 532 nm and fast response speed of 50 ms. Moreover, field effect regulation allows for further improvement of the photoresponse performance of the heterojunction field effect transistor device, where the responsivity can be increased to 3.34 × 103 A W-1 with a 60 V gate voltage. Overall, the one-step vdW epitaxy process is a promising and convenient route towards constructing high quality Bi2 O2 Se based heterojunction for improving its photodetection performance.

Epitaxial Growth of 2D Ultrathin Metastable γ-Bi2 O3 Flakes for High Performance Ultraviolet Photodetection.

Ultraviolet detection is of great significance due to its wide applications in the missile tracking, flame detecting, pollution monitoring, and so on. The nonlayered semiconductor γ-Bi2 O3 is a promising candidate toward high-performance UV detection due to the wide bandgap, excellent light sensitivity, environmental stability, nontoxic and elemental abundance properties. However, controllable preparation of ultrathin 2D γ-Bi2 O3 flakes remains a challenge, owing to its nonlayered structure, metastable nature, and other competing phases. Moreover, the UV photodetectors based on 2D γ-Bi2 O3 flake have not been implemented yet. Here, ultrathin (down to 4.8 nm) 2D γ-Bi2 O3 flakes with high crystal quality are obtained via a van der Waals epitaxy method. The as-synthesized single-crystalline γ-Bi2 O3 flakes show a body-centered cubic structure and grown along (111) lattice plane as revealed by experimental observations. More importantly, photodetectors based on the as-synthesized 2D γ-Bi2 O3 flakes exhibit promising UV detection ability, including a responsivity of 64.5 A W-1 , a detectivity of 1.3 × 1013 Jones, and an ultrafast response speed (τrise  ≈ 290 µs and τdecay  ≈ 870 µs) at 365 nm, suggesting its great potential for various optoelectronic applications.

Surface Vacancy-Induced Switchable Electric Polarization and Enhanced Ferromagnetism in Monolayer Metal Trihalides.

Monolayer chromium triiodide (CrI3), as the thinnest ferromagnetic material demonstrated in experiment [ Huang et al. Nature 2017 , 546 , 270 ], opens up new opportunities for the application of two-dimensional (2D) materials in spintronic nanodevices. Atom-thick 2D materials with switchable electric polarization are now urgently needed for their rarity and important roles in nanoelectronics. Herein, we unveil that surface I vacancies not only enhance the intrinsic ferromagnetism of monolayer CrI3 but also induce switchable electric polarization. I vacancies bring about an out-of-plane polarization without breaking the nonmetallic nature of CrI3. Meanwhile, the induced polarization can be reversed in a moderate energy barrier, arising from the unique porosity of CrI3 that contributes to the switch of I vacancies between top and bottom surfaces. Engineering 2D switchable polarization through surface vacancies is also applicable to many other metal trihalides, which opens up a new and general way toward pursuing low-dimensional multifunctional nanodevices.

Precise, Self-Limited Epitaxy of Ultrathin Organic Semiconductors and Heterojunctions Tailored by van der Waals Interactions.

Precise assembly of semiconductor heterojunctions is the key to realize many optoelectronic devices. By exploiting the strong and tunable van der Waals (vdW) forces between graphene and organic small molecules, we demonstrate layer-by-layer epitaxy of ultrathin organic semiconductors and heterostructures with unprecedented precision with well-defined number of layers and self-limited characteristics. We further demonstrate organic p-n heterojunctions with molecularly flat interface, which exhibit excellent rectifying behavior and photovoltaic responses. The self-limited organic molecular beam epitaxy (SLOMBE) is generically applicable for many layered small-molecule semiconductors and may lead to advanced organic optoelectronic devices beyond bulk heterojunctions.

Towards a Comprehensive Understanding of the Reaction Mechanisms Between Defective MoS2 and Thiol Molecules.

Sulfur vacancies (SVs) inherent in MoS2 are generally detrimental for carrier mobility and optical properties. Thiol chemistry has been explored for SV repair and surface functionalization. However, the resultant products and reaction mechanisms are still controversial. Herein, a comprehensive understanding on the reactions is provided by tracking potential energy surfaces and kinetic studies. The reactions are dominated by two competitive mechanisms that lead to either functionalization products or repair SVs, and the polarization effect from decorating thiol molecules and thermal effect are two determining factors. Electron-donating groups are conducive to the repairing reaction whereas electron-withdrawing groups facilitate the functionalization process. Moreover, the predominant reaction mechanism can be switched by increasing the temperature. This study fosters a way of precisely tailoring the electronic and optical properties of MoS2 by means of thiol chemistry approaches.

Ultrahigh Responsivity and Robust Semiconducting Fiber Enabled by Molecular Soldering-Governed Defect Engineering for Smart Textile Optoelectronics.

Semiconducting fibers (SCFs) are of significant interest to design next-generation wearable and comfortable optoelectronics that seamlessly integrate with textiles. However, the practical applications of current SCFs are always limited by poor optoelectronic performance and low mechanical robustness caused by uncontrollable multiscale structural defects. Herein, a versatile in situ molecular soldering-governed defect engineering strategy is proposed to construct ultrahigh responsivity and robust wet-spun MoS2 SCFs, by using a π-conjugated dithiolated molecule to simultaneously patch microscale sulfur vacancies within MoS2 nanosheets, diminish mesoscale interlayer voids/wrinkles, promote macroscale orientation, build long-range photoelectron percolation bridges, and provide n-doping effect. The derived MoS2 SCFs exhibit over two orders of magnitude higher responsivity (144.3 A W-1) than previously reported fiber photodetectors, 37.3-fold faster photoresponse speed (52 ms) than pristine counterpart, and remarkable bending robustness (retain 94.2% of the initial photocurrent after 50 000 bending-flattening cycles). Such superior robustness and photodetection capacity of MoS2 SCFs further enable large-scale weaving of reliable smart textile optoelectronic systems, such as direction-identifiable wireless light alarming system, modularized mechano-optical communication system, and indoor light-controlled IoT system. This work offers a universal strategy for the scalable production of mechanically robust and high-performance SCFs, opening up exciting possibilities for large-scale integration of wearable optoelectronics.

Improving the Sensitivity of Task-Based Multi-Echo Functional Magnetic Resonance Imaging via T2* Mapping Using Synthetic Data-Driven Deep Learning.

(1) Background: Functional magnetic resonance imaging (fMRI) utilizing multi-echo gradient echo-planar imaging (ME-GE-EPI) has demonstrated higher sensitivity and stability compared to utilizing single-echo gradient echo-planar imaging (SE-GE-EPI). The direct derivation of T2* maps from fitting multi-echo data enables accurate recording of dynamic functional changes in the brain, exhibiting higher sensitivity than echo combination maps. However, the widely employed voxel-wise log-linear fitting is susceptible to inevitable noise accumulation during image acquisition. (2) Methods: This work introduced a synthetic data-driven deep learning (SD-DL) method to obtain T2* maps for multi-echo (ME) fMRI analysis. (3) Results: The experimental results showed the efficient enhancement of the temporal signal-to-noise ratio (tSNR), improved task-based blood oxygen level-dependent (BOLD) percentage signal change, and enhanced performance in multi-echo independent component analysis (MEICA) using the proposed method. (4) Conclusion: T2* maps derived from ME-fMRI data using the proposed SD-DL method exhibit enhanced BOLD sensitivity in comparison to T2* maps derived from the LLF method.

Enhancing crystal integrity and structural rigidity of CsPbBr3 nanoplatelets to achieve a narrow color-saturated blue emission.

Quantum-confined CsPbBr3 perovskites are promising blue emitters for ultra-high-definition displays, but their soft lattice caused by highly ionic nature has a limited stability. Here, we endow CsPbBr3 nanoplatelets (NPLs) with atomic crystal-like structural rigidity through proper surface engineering, by using strongly bound N-dodecylbenzene sulfonic acid (DBSA). A stable, rigid crystal structure, as well as uniform, orderly-arranged surface of these NPLs is achieved by optimizing intermediate reaction stage, by switching from molecular clusters to mono-octahedra, while interaction with DBSA resulted in formation of a CsxO monolayer shell capping the NPL surface. As a result, both structural and optical stability of the CsPbBr3 NPLs is enhanced by strong covalent bonding of DBSA, which inhibits undesired phase transitions and decomposition of the perovskite phase potentially caused by ligand desorption. Moreover, rather small amount of DBSA ligands at the NPL surface results in a short inter-NPL spacing in their closely-packed films, which facilitates efficient charge injection and transport. Blue photoluminescence of the produced CsPbBr3 NPLs is bright (nearly unity emission quantum yield) and peaks at 457 nm with an extremely narrow bandwidth of 3.7 nm at 80 K, while the bandwidth of the electroluminescence (peaked at 460 nm) also reaches a record-narrow value of 15 nm at room temperature. This value corresponds to the CIE coordinates of (0.141, 0.062), which meets Rec. 2020 standards for ultra-high-definition displays.

Building intercalation structure for high ionic conductivity via aliovalent substitution.

Two-dimensional (2D) materials, which possess robust nanochannels, high flux and allow scalable fabrication, provide new platforms for nanofluids. Highly efficient ionic conductivity can facilitate the application of nanofluidic devices for modern energy conversion and ionic sieving. Herein, we propose a novel strategy of building an intercalation crystal structure with negative surface charge and mobile interlamellar ions via aliovalent substitution to boost ionic conductivity. The Li2xM1-xPS3 (M = Cd, Ni, Fe) crystals obtained by the solid-state reaction exhibit distinct capability of water absorption and apparant variation of interlayer spacing (from 0.67 to 1.20 nm). The assembled membranes show the ultrahigh ionic conductivity of 1.20 S/cm for Li0.5Cd0.75PS3 and 1.01 S/cm for Li0.6Ni0.7PS3. This facile strategy may inspire the research in other 2D materials with higher ionic transport performance for nanofluids.

Active and conductive layer stacked superlattices for highly selective CO2 electroreduction.

Metal oxides are archetypal CO2 reduction reaction electrocatalysts, yet inevitable self-reduction will enhance competitive hydrogen evolution and lower the CO2 electroreduction selectivity. Herein, we propose a tangible superlattice model of alternating metal oxides and selenide sublayers in which electrons are rapidly exported through the conductive metal selenide layer to protect the active oxide layer from self-reduction. Taking BiCuSeO superlattices as a proof-of-concept, a comprehensive characterization reveals that the active [Bi2O2]2+ sublayers retain oxidation states rather than their self-reduced Bi metal during CO2 electroreduction because of the rapid electron transfer through the conductive [Cu2Se2]2- sublayer. Theoretical calculations uncover the high activity over [Bi2O2]2+ sublayers due to the overlaps between the Bi p orbitals and O p orbitals in the OCHO* intermediate, thus achieving over 90% formate selectivity in a wide potential range from -0.4 to -1.1 V. This work broadens the studying and improving of the CO2 electroreduction properties of metal oxide systems.

Scalable Van der Waals Encapsulation by Inorganic Molecular Crystals.

Encapsulation is critical for devices to guarantee their stability and reliability. It becomes an even more essential requirement for devices based on 2D materials with atomic thinness and far inferior stability compared to their bulk counterparts. Here a general van der Waals (vdW) encapsulation method for 2D materials using Sb2 O3 layer of inorganic molecular crystal fabricated via thermal evaporation deposition is reported. It is demonstrated that such a scalable encapsulation method not only maintains the intrinsic properties of typical air-susceptible 2D materials due to their vdW interactions but also remarkably improves their environmental stability. Specifically, the encapsulated black phosphorus (BP) exhibits greatly enhanced structural stability of over 80 days and more sustaining-electrical properties of 19 days, while the bare BP undergoes degradation within hours. Moreover, the encapsulation layer can be facilely removed by sublimation in vacuum without damaging the underlying materials. This scalable encapsulation method shows a promising pathway to effectively enhance the environmental stability of 2D materials, which may further boost their practical application in novel (opto)electronic devices.

Single WTe2 Sheet-Based Electrocatalytic Microdevice for Directly Detecting Enhanced Activity of Doped Electronegative Anions.

The high electrical conductivity of 1T'-WTe2 deserves particular attention and may show a high potential for hydrogen evolution reaction (HER) catalysis. However, the actual activity certainly does not match expectations, and the inferior HER activity is actually still ambiguous at the atomic level. Unraveling the underlying HER behaviors of 1T'-WTe2 will give rise to a new family of HER catalysts. Our structural analysis reveals that the inferior activity could result from insufficient charge density around the Te site and blocked adsorption channel at the W site, which cause too weak hydrogen adsorption. Herein, we fabricated a single WTe2 sheet-based electrocatalytic microdevice for directly extracting enhanced HER activity of doped electronegative F atoms. The overpotential at -10 mA cm-2 reduced to 0.27 V after F doping compared to 0.45 V for the original state. In situ electrochemical measurement and electrical tests on a single sheet indicate that doped F can regulate surface charge and hydrogen adsorption behavior. Furthermore, the theory simulation uncovers that the smaller atomic radius of F contributes to an empty coordination environment; meanwhile, strong electronegativity induces hydrogen adsorption. Thus, the ΔGH* at W sites around the doped F is as low as 0.18 eV. Synergistically modulating the charge properties and opening steric hindrance provides a new pathway to rationally construct electrocatalysts and beyond.

A Universal Atomic Substitution Conversion Strategy Towards Synthesis of Large-Size Ultrathin Nonlayered Two-Dimensional Materials.

Nonlayered two-dimensional (2D) materials have attracted increasing attention, due to novel physical properties, unique surface structure, and high compatibility with microfabrication technique. However, owing to the inherent strong covalent bonds, the direct synthesis of 2D planar structure from nonlayered materials, especially for the realization of large-size ultrathin 2D nonlayered materials, is still a huge challenge. Here, a general atomic substitution conversion strategy is proposed to synthesize large-size, ultrathin nonlayered 2D materials. Taking nonlayered CdS as a typical example, large-size ultrathin nonlayered CdS single-crystalline flakes are successfully achieved via a facile low-temperature chemical sulfurization method, where pre-grown layered CdI2 flakes are employed as the precursor via a simple hot plate assisted vertical vapor deposition method. The size and thickness of CdS flakes can be controlled by the CdI2 precursor. The growth mechanism is ascribed to the chemical substitution reaction from I to S atoms between CdI2 and CdS, which has been evidenced by experiments and theoretical calculations. The atomic substitution conversion strategy demonstrates that the existing 2D layered materials can serve as the precursor for difficult-to-synthesize nonlayered 2D materials, providing a bridge between layered and nonlayered materials, meanwhile realizing the fabrication of large-size ultrathin nonlayered 2D materials.

Enhanced Ferromagnetism and Tunable Magnetism in Fe3GeTe2 Monolayer by Strain Engineering.

Recent discovery of intrinsic ferromagnetism in Fe3GeTe2 (FGT) monolayer [Deng, Y.; Nature 2018, 563, 94-99; Fei, Z.; Nat. Mater. 2018, 17, 778-782] not only extended the family of two-dimensional (2D) magnetic materials but also stimulated further interest in the possibility to tune their magnetic properties without changing the chemical composition or introducing defects. By means of density functional theory computations, we explore strain effects on the magnetic properties of the FGT monolayer. We demonstrate that the ferromagnetism can be largely enhanced by the tensile strain in the FGT monolayer due to the competitive effects of direct exchange and superexchange interaction. The average magnetic moments of Fe atoms increase monotonically with an increase in biaxial strain from -5 to 5% in FGT monolayer. The intriguing variation of magnetic moments with strain in the FGT monolayer is related to the charge transfer induced by the changes in the bond lengths. Given the successful fabrication of the FGT monolayer, the strain-tunable ferromagnetism in the FGT monolayer can stimulate the experimental effort in this field. This work also suggests an effective route to control the magnetic properties of the FGT monolayer. The pronounced magnetic response toward the biaxial strain can be used to design the magnetomechanical coupling spintronics devices based on FGT.